Chemical synthesis is essential in industries such as petrochemicals, fine chemicals, and pharmaceuticals, driving economic and social development. The increasing demand for new molecules and materials calls for novel...Chemical synthesis is essential in industries such as petrochemicals, fine chemicals, and pharmaceuticals, driving economic and social development. The increasing demand for new molecules and materials calls for novel chemical reactions;however, manual experimental screening is time-consuming. Artificial intelligence (AI) offers a promising solution by leveraging large-scale experimental data to model chemical reactions, although challenges such as the lack of standardization and predictability in chemical synthesis hinder AI applications. Additionally, the multi-scale nature of chemical reactions, along with complex multiphase processes, further complicates the task. Recent advances in microchemical systems, particularly continuous flow methods using microreactors, provide precise control over reaction conditions, enhancing reproducibility and enabling high-throughput experimentation. These systems minimize transport-related inconsistencies and facilitate scalable industrial applications. This review systematically explores recent developments in intelligent synthesis based on microchemical systems, focusing on reaction system design, synthesis robots, closed-loop optimization, and high-throughput experimentation, while identifying key areas for future research.展开更多
All-solid-state lithium batteries(ASSLBs)are strongly considered as the next-generation energy storage devices for their high energy density and intrinsic safety.The solid-solid contact between lithium metal and solid...All-solid-state lithium batteries(ASSLBs)are strongly considered as the next-generation energy storage devices for their high energy density and intrinsic safety.The solid-solid contact between lithium metal and solid electrolyte plays a vital role in the performance of working ASSLBs,which is challenging to investigate quantitatively by experimental approach.This work proposed a quantitative model based on the finite element method for electrochemical impedance spectroscopy simulation of different solid-solid contact states in ASSLBs.With the assistance of an equivalent circuit model and distribution of relaxation times,it is discovered that as the number of voids and the sharpness of cracks increase,the contact resistance Rcgrows and ultimately dominates the battery impedance.Through accurate fitting,inverse proportional relations between contact resistance Rcand(1-porosity)as well as crack angle was disclosed.This contribution affords a fresh insight into clarifying solid-solid contact states in ASSLBs.展开更多
Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illust...Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illustrated the morphological fates of waste leaf-derived graphitic carbon(WLGC)produced from waste ginkgo leaves via pyrolysis temperature regulation and used as bifunctional cathode catalyst for simultaneous H_(2)O_(2) electrochemical generation and organic pollutant degradation,discovering S/N-self-doping shown to facilitate a synergistic effect on reactive oxygen species(ROS)generation.Under the optimum temperature of 800℃,the WLGC exhibited a H_(2)O_(2) selectivity of 94.2%and tetracycline removal of 99.3%within 60 min.Density functional theory calculations and in-situ Fourier transformed infrared spectroscopy verified that graphitic N was the critical site for H_(2)O_(2) generation.While pyridinic N and thiophene S were the main active sites responsible for OH generation,N vacancies were the active sites to produce ^(1)O_(2) from O_(2).The performance of the novel cathode for tetracycline degradation remains well under a wide pH range(3–11),maintaining excellent stability in 10 cycles.It is also industrially applicable,achieving satisfactory performance treating in real water matrices.This system facilitates both radical and non-radical degradation,offering valuable advances in the preparation of cost-effective and sustainable electrocatalysts and hold strong potentials in metal-free EAOPs for organic pollutant degradation.展开更多
Cardiac tissue engineering aims to efficiently replace or repair injured heart tissue using scaffolds,relevant cells,or their combination.While the combination of scaffolds and relevant cells holds the potential to ra...Cardiac tissue engineering aims to efficiently replace or repair injured heart tissue using scaffolds,relevant cells,or their combination.While the combination of scaffolds and relevant cells holds the potential to rapidly remuscularize the heart,thereby avoiding the slow process of cell recruitment,the proper ex vivo cellularization of a scaffold poses a substantial challenge.First,proper diffusion of nutrients and oxygen should be provided to the cell-seeded scaffold.Second,to generate a functional tissue construct,cells can benefit from physiological-like conditions.To meet these challenges,we developed a modular bioreactor for the dynamic cellularization of full-thickness cardiac scaffolds under synchronized mechanical and electrical stimuli.In this unique bioreactor system,we designed a cyclic mechanical load that mimics the left ventricle volume inflation,thus achieving a steady stimulus,as well as an electrical stimulus with an action potential profile to mirror the cells’microenvironment and electrical stimuli in the heart.These mechanical and electrical stimuli were synchronized according to cardiac physiology and regulated by constant feedback.When applied to a seeded thick porcine cardiac extracellular matrix(pcECM)scaffold,these stimuli improved the proliferation of mesenchymal stem/stromal cells(MSCs)and induced the formation of a dense tissue-like structure near the scaffold’s surface.Most importantly,after 35 d of cultivation,the MSCs presented the early cardiac progenitor markers Connexin-43 andα-actinin,which were absent in the control cells.Overall,this research developed a new bioreactor system for cellularizing cardiac scaffolds under cardiac-like conditions,aiming to restore a sustainable dynamic living tissue that can bear the essential cardiac excitation–contraction coupling.展开更多
Lignocellulosic biomass is one of the viable solutions to alleviate the global warming. However, the limited utilization of biomass majorly focused on cellulose and hemicellulose restricts the economic and environment...Lignocellulosic biomass is one of the viable solutions to alleviate the global warming. However, the limited utilization of biomass majorly focused on cellulose and hemicellulose restricts the economic and environmental feasibilities. To cope with this issue, we proposed an integrated process of co-producing 1,6-hexanediol(1,6-HDO) with tetrahydrofuran and adipic acid from biomass, referred to as Strategy A. To compare the impacts of lignin upgrading and feedstock, Strategy B, which co-produces tetrahydrofuran alone, and Strategy C, which is the traditional route to produce 1,6-HDO from fossil fuels, were used. Heat networks are also designed to reduce operating costs and indirect carbon emissions due to energy consumption, saving 87% and 83% of the heat and cooling requirements, respectively, in Strategy A. The market competitiveness of Strategy A was evaluated by determining the minimum selling price through techno-economic analysis, and sustainability was thoroughly investigated by quantifying the environmental impacts through both midpoint and endpoint life-cycle assessments(LCAs).Strategy A was found to be the most favorable both economically(USRDSCHARDOLLAR3,402/ton) and environmentally(-26.9 kg CO_(2)eq.). This indicates that lignin valorization is not only economically but also environmentally preferred. Finally, changes in economic and environmental feasibilities depending on economic, process, and environmental parameters were investigated using sensitivity and uncertainty analyses. The results of these analyses provide valuable insight into bio-based chemical production.展开更多
In pursuit of meeting the demands for the next generation of high energy density and flexible electronic products,there is a growing interest in flexible energy storage devices.Silicon(Si)stands out as a promising ele...In pursuit of meeting the demands for the next generation of high energy density and flexible electronic products,there is a growing interest in flexible energy storage devices.Silicon(Si)stands out as a promising electrode material due to its high theoretical specific capacity(~3579 mA h g^(-1)),low lithiation potential(~0.40 V),and abundance in nature.We have successfully developed freestanding and flexible CNT/Si/low-melting-point metal(LM)electrodes,which obviate the need for conductive additives,adhesives,and thereby increase the energy density of the device.As an anode material for lithium-ion batteries(LIBs),the CNT/Si/LM electrode demonstrates remarkable cycling stability and rate performance,achieving a reversible capacity of 1871.8 mA h g^(-1)after 100 cycles at a current density of 0.2 A g^(-1).In-situ XRD and in-situ thickness analysis are employed to elucidate the underlying mechanisms during the lithiation/delithiation.Density functional theory(DFT)calculations further substantiate the mechanism by which LM enhances the electrochemical performance of Si,focusing on the aspects of stress mitigation and reduction of the diffusion energy barrier.This research introduces a novel approach to flexible electrode design by integrating CNT films,LM,and Si,thereby charting a path forward for the development of next-generation flexible LIBs.展开更多
Hydrophilicity is critical in Nafion membranes during fuel cell operation as insufficient membrane hydration leads to brittle behavior and a drop in proton conductivity.The incorporation of APTS(3-(aminopro pyl)trieth...Hydrophilicity is critical in Nafion membranes during fuel cell operation as insufficient membrane hydration leads to brittle behavior and a drop in proton conductivity.The incorporation of APTS(3-(aminopro pyl)triethoxysilane)into exfoliated graphene oxide(EGO)by covalent functionalization to be used as filler into Nafion membranes allows higher hydrophilicity for these membranes.This is associated with promoting hydroxyl,carbonyl,siloxane,silane,and amine groups within the EGO-APTS matrix.The incorporation of these materials as Fuel Cell MEAs leads to a significant reduction of the ohmic resistance measured at high frequency resistance(HFR)in electrochemical impedance spectroscopy(EIS)experiments and achieves maximum power densities of 1.33 W cm^(-2)at 60℃ at 100%RH(APTS-EGO,0.2 wt%)and1.33 W cm^(-2)at 60℃ at 70%RH(APTS-EGO,0.3 wt%),which represents an improvement of 190%compared to the commercial Nafion 212 when utilizing low humidification conditions(70%).Moreover,the as-synthesized membrane utilizes lower Nafion ionomer mass,which,in conjunction with the excellent cell performance,has the potential to decrease the cost of the membrane from 87 to 80￡/W as well as a reduction of fluorinated compounds within the membrane.展开更多
Metal-sulfur electrochemistry represents a promising energy storage technology due to the natural abundance and unparalleled theoretical specific capacity of 1675 mAh g^(-1)of sulfur based on two-electron redox reacti...Metal-sulfur electrochemistry represents a promising energy storage technology due to the natural abundance and unparalleled theoretical specific capacity of 1675 mAh g^(-1)of sulfur based on two-electron redox reaction(S^(0)■S^(2-)).Commercially viable metal-sulfur batteries(MSBs)are hindered by sluggish sulfur conversion kinetics,which reduce the utilization efficiency of sulfur and lead to polysulfide shuttling.Single-atom catalysts(SACs)exhibit specific catalytic activity,a high atomic utilization ratio,and flexible selectivity,and are considered exceptional electrocatalysts for addressing the intractable challenges encountered by the MSBs.This review summarizes the recent progress in SACs for boosting the sulfur electrochemistry in MSBs,focusing on sulfur host materials,modified separators and functional interlayers,and analyzes the in-depth mechanisms of SACs.Moreover,the correlation between the coordination environments and the intrinsic activity of SACs is discussed.Finally,the main challenges and potential research directions of SACs for high-energy-density and long-life MSBs are outlined.This study provides significant guidance for constructing novel SACs that can accelerate the sulfur conversion kinetics in MSBs.展开更多
Recently,potassium-ion batteries(PIBs)have received significant attention in the energy storage field owing to their high-power output,fast charging capability,natural abundance,and environmental sustainability.Herein...Recently,potassium-ion batteries(PIBs)have received significant attention in the energy storage field owing to their high-power output,fast charging capability,natural abundance,and environmental sustainability.Herein,we comprehensively review recent advancements in the design and development of carbon-based anode materials for PIBs anodes,covering graphite,hard carbon,alloy and conversion materials with carbon,and carbon host for K metal deposition.Chemical strategies such as structural engineering,heteroatom-doping,and surface modifications are highlighted to improve electrochemical performances as well as to resolve technical challenges,such as electrode instability,low initial Coulombic efficiency,and electrolyte compatibility.Furthermore,we discuss the fundamental understanding of potassium-ion storage mechanisms of carbon-based materials and their correlation with electrochemical performance.Finally,we present the current challenges and future research directions for the practical implementation of carbon-based anodes to enhance their potential as next-generation energy storage materials for PIBs.This review aims to provide our own insights into innovative design strategies for advanced PIB's anode through the chemical and engineering strategies.展开更多
Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined acti...Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.展开更多
Various novel conjugated polymers(CPs)have been developed for organic photodetectors(OPDs),but their application to practical image sensors such as X-ray,R/G/B,and fingerprint sensors is rare.In this article,we report...Various novel conjugated polymers(CPs)have been developed for organic photodetectors(OPDs),but their application to practical image sensors such as X-ray,R/G/B,and fingerprint sensors is rare.In this article,we report the entire process from the synthesis and molecular engineering of novel CPs to the development of OPDs and fingerprint image sensors.We synthesized six benzo[1,2-d:4,5-d’]bis(oxazole)(BBO)-based CPs by modifying the alkyl side chains of the CPs.Several relationships between the molecular structure and the OPD performance were revealed,and increasing the number of linear octyl side chains on the conjugated backbone was the best way to improve Jph and reduce Jd in the OPDs.The optimized CP demonstrated promising OPD performance with a responsivity(R)of 0.22 A/W,specific detectivity(D^(*))of 1.05×10^(13)Jones at a bias of-1 V,rising/falling response time of 2.9/6.9μs,and cut-off frequency(f_(-3dB))of 134 kHz under collimated 530 nm LED irradiation.Finally,a fingerprint image sensor was fabricated by stacking the POTB1-based OPD layer on the organic thin-film transistors(318 ppi).The image contrast caused by the valleys and ridges in the fingerprints was obtained as a digital signal.展开更多
Polymer binders possess significant potential in alleviating the volume expansion issues of silicon-based anodes,yet remain challenging due to insufficient interfacial interactions with individual components(Si,C,and ...Polymer binders possess significant potential in alleviating the volume expansion issues of silicon-based anodes,yet remain challenging due to insufficient interfacial interactions with individual components(Si,C,and Cu)of the anode.Herein,we report the synthesis of a stable three-dimensional network structure of the PAA-PEA(polyacrylic acid-polyether amines)polymer binder through intermolecular physicochemical dual cross-linking.By incorporating polar functional groups,the binder molecules not only form strong C-O-Si,N-Si,O=C-O-C,and O=C-O-Cu covalent bonds but also enhance non-covalent interactions with Si,C,and Cu,thereby improving adhesion between the binder and each interface of the anode.Furthermore,weak hydrogen bonds,acting as"sacrificial bonds",dissipate energy and disperse accumulated stress,improving the material flexibility.Due to the high mechanical stability of the framework,which combines both rigidity and flexibility and the coupling effect at the three interfaces,the movement and separation of electrode components are effectively restrained,significantly enhancing the cycling stability of silicon-graphite anodes.The PAA-PEA 2000 electrode exhibits a capacity retention of 78% after 500 cycles at a current density of 0.2 A g^(-1).This work provides insights into the mechanism of binders and guides the design of polymer binders for high-performance Si-based electrodes.展开更多
Integrating multiple modalities of cancer therapies for synergistic and enhanced therapeutic efficacy remains challenging.Herein,flash nanoprecipitation(FNP),a kinetically driven process,was employed to expedite the c...Integrating multiple modalities of cancer therapies for synergistic and enhanced therapeutic efficacy remains challenging.Herein,flash nanoprecipitation(FNP),a kinetically driven process,was employed to expedite the coordination reaction time required for nano-encapsulate components with completely opposite physiochemical properties including sorafenib(SRF),hemoglobin(Hb),chlorin e6(Ce6),and indocyanine green(ICG)into a multi-component HSCI nanomedicine.Hydrophilic components Hb and ICG interact to form hydrophobic ICG-Hb complexes under electrostatic and hydrophobic interactions.This process facilitates the characteristic time of nucleation(τ_(nucleation))to match the characteristic mixing time(τ_(mix))of the FNP process,resulting in the formulation of kinetically stable nanomedicine,overcoming the long equilibrium times and instability issues associated with thermodynamic assembly.Importantly,pH-responsive structure is also easily but effectively integrated in nanomedicine during this kinetically driven formulation to manipulate its structures.In the acidic tumor microenvironment(TME),the pH-stimulated morphology transformation of HSCI nanomedicine boosts its reactive oxygen species(ROS)generation efficiency and photothermal efficacy,endowing it with better antitumor suppression.In vitro and in vivo experiments reveal that the HSCI nanomedicine offers a synergistic therapeutic effect and stronger tumor suppression compared with single therapies.These results open a new window for developing strategies for multimodal combinatory cancer therapies.展开更多
Plant cell wall(CW)-like soft materials,referred to as artificial CWs,are composites of assembled polymers containing micro-/nanoparticles or fibers/fibrils that are designed to mimic the composition,structure,and mec...Plant cell wall(CW)-like soft materials,referred to as artificial CWs,are composites of assembled polymers containing micro-/nanoparticles or fibers/fibrils that are designed to mimic the composition,structure,and mechanics of plant CWs.CW-like materials have recently emerged to test hypotheses pertaining to the intricate structure–property relationships of native plant CWs or to fabricate functional materials.Here,research on plant CWs and CW-like materials is reviewed by distilling key studies on biomimetic composites primarily composed of plant polysaccharides,including cellulose,pectin,and hemicellulose,as well as organic polymers like lignin.Micro-and nanofabrication of plant CW-like composites,characterization techniques,and in silico studies are reviewed,with a brief overview of current and potential applications.Micro-/nanofabrication approaches include bacterial growth and impregnation,layer-by-layer assembly,film casting,3-dimensional templating microcapsules,and particle coating.Various characterization techniques are necessary for the comprehensive mechanical,chemical,morphological,and structural analyses of plant CWs and CW-like materials.CW-like materials demonstrate versatility in real-life applications,including biomass conversion,pulp and paper,food science,construction,catalysis,and reaction engineering.This review seeks to facilitate the rational design and thorough characterization of plant CW-mimetic materials,with the goal of advancing the development of innovative soft materials and elucidating the complex structure–property relationships inherent in native CWs.展开更多
Magnesium(Mg)-based bioresorbable stents represent a potentially groundbreaking advancement in cardiovascular therapy;offering tem-porary vessel support and complete biodegradability—addressing limitations of traditi...Magnesium(Mg)-based bioresorbable stents represent a potentially groundbreaking advancement in cardiovascular therapy;offering tem-porary vessel support and complete biodegradability—addressing limitations of traditional stents like in-stent restenosis and long-term com-plications.However,challenges such as rapid corrosion and suboptimal endothelialisation have hindered their clinical adoption.This review highlights the latest breakthroughs in surface modification,alloying,and coating strategies to enhance the mechanical integrity,corrosion resistance,and biocompatibility of Mg-based stents.Key surface engineering techniques,including polymer and bioactive coatings,are ex-amined for their role in promoting endothelial healing and minimising inflammatory responses.Future directions are proposed,focusing on personalised stent designs to optimize efficacy and long-term outcomes,positioning Mg-based stents as a transformative solution in interventional cardiology.展开更多
Dry reforming of methane(DRM)over Ni-based catalysts is an economically reasonable technology for large-scale CO_(2)utilization.However,prolonged Ni sintering and carbon deposition reduce the durability and efficiency...Dry reforming of methane(DRM)over Ni-based catalysts is an economically reasonable technology for large-scale CO_(2)utilization.However,prolonged Ni sintering and carbon deposition reduce the durability and efficiency of DRM,hindering its engineering application.Herein,we propose a facile approach by combining continuous microscale coprecipitation with solid-state reactions to construct a BaAl_(2)O_(4)-overlayer-confined Ni catalyst.The 5-wt%-Ni@BaAl_(2)O_(4)catalyst exhibited advanced CO_(2)and CH_(4)conversions of 96% and 86% at 800℃ and a GHSV of 144 L g_(cat)^(-1).h^(-1).Moreover,the k_(d)-CO_(2)and k_(d)-CH_(4)of Ni@BaAl_(2)O_(4)were 0.0063 and 0.0029 h^(-1);which are approximately half and one-thirds of those of Ni/BaAl_(2)O_(4)and slightly better than those of Ni@MgAl_(2)O_(4),underscoring the versatility of the proposed synthesis protocol for constructing core-shell structures.XAS,HAADF-STEM-EDS,and CO transmission-IR characterizations confirmed the SMSI of~2-nm amorphous BaAl_(2)O_(4)-overlaid~10 nm Ni with an overall mesoporous structure.After a long-term test,the sintering and coking inhibition effects of Ni@BaAl_(2)O_(4)(10→11 nm,0.55 mgCg_(cat)^(-1).h^(-1))outperformed Ni/BaAl_(2)O_(4)(13→22 nm,1.90 mgCg_(cat)^(-1).h^(-1))and Ni@MgAl_(2)O_(4).In situ time-resolved CH4→CO_(2)transient response,DRIFTS experiments,and DFT calculations suggested that Ni@BaAl_(2)O_(4)and Ni/BaAl_(2)O_(4)followed the Mars-van Krevelen and Langmuir-Hinshelwood redox mechanisms,respectively.The functional interfacial lattice oxygen promoted the removal of C_(ads)^(*)on Ni and core-shell structure induced fast CO_(2)adsorption and CO desorption.The present study provides a facile approach for constructing a stable and active Ni-based core-shell catalyst.Furthermore,it offers novel insights into the functionalities of non-reducible spinel overlayers in the DRM process.展开更多
CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synerg...CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.展开更多
This study investigates the electrochemical behavior of molybdenum disulfide(MoS_(2))as an anode in Li-ion batteries,focusing on the extra capacity phenomenon.Employing advanced characterization methods such as in sit...This study investigates the electrochemical behavior of molybdenum disulfide(MoS_(2))as an anode in Li-ion batteries,focusing on the extra capacity phenomenon.Employing advanced characterization methods such as in situ and ex situ X-ray diffraction,Raman spectroscopy,X-ray photoelectron spectroscopy,and transmission electron microscopy,the research unravels the complex structural and chemical evolution of MoS_(2) throughout its cycling.A key discovery is the identification of a unique Li intercalation mechanism in MoS_(2),leading to the formation of reversible Li_(2)MoS_(2) phases that contribute to the extra capacity of the MoS_(2) electrode.Density function theory calculations suggest the potential for overlithiation in MoS_(2),predicting Li5MoS_(2) as the most energetically favorable phase within the lithiation–delithiation process.Additionally,the formation of a Li-rich phase on the surface of Li_(4)MoS_(2) is considered energetically advantageous.After the first discharge,the battery system engages in two main reactions.One involves operation as a Li-sulfur battery within the carbonate electrolyte,and the other is the reversible intercalation and deintercalation of Li in Li_(2)MoS_(2).The latter reaction contributes to the extra capacity of the battery.The incorporation of reduced graphene oxide as a conductive additive in MoS_(2) electrodes notably improves their rate capability and cycling stability.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
This paper discussed an extended model for flexibility analysis of chemical process. Under uncertainty, probability density function is used to describe uncertain parameters instead of hyper-rectangle, and chanceconst...This paper discussed an extended model for flexibility analysis of chemical process. Under uncertainty, probability density function is used to describe uncertain parameters instead of hyper-rectangle, and chanceconstrained programming is a feasible way to deal with the violation of constraints. Because the feasible region of control variables would change along with uncertain parameters, its smallest acceptable size threshold is presented to ensure the controllability condition. By synthesizing the considerations mentioned above, a modified model can describe the flexibility analysis problem more exactly. Then a hybrid algorithm, which integrates stochastic simulation and genetic algorithm, is applied to solve this model and maximize the flexibility region. Both numerical and chemical process examples are presented to demonstrate the effectiveness of the method.展开更多
基金supported by the National Natural Science Foundation of China(22378227)Shijiazhuang Science and Technology Bureau(231790163A).
文摘Chemical synthesis is essential in industries such as petrochemicals, fine chemicals, and pharmaceuticals, driving economic and social development. The increasing demand for new molecules and materials calls for novel chemical reactions;however, manual experimental screening is time-consuming. Artificial intelligence (AI) offers a promising solution by leveraging large-scale experimental data to model chemical reactions, although challenges such as the lack of standardization and predictability in chemical synthesis hinder AI applications. Additionally, the multi-scale nature of chemical reactions, along with complex multiphase processes, further complicates the task. Recent advances in microchemical systems, particularly continuous flow methods using microreactors, provide precise control over reaction conditions, enhancing reproducibility and enabling high-throughput experimentation. These systems minimize transport-related inconsistencies and facilitate scalable industrial applications. This review systematically explores recent developments in intelligent synthesis based on microchemical systems, focusing on reaction system design, synthesis robots, closed-loop optimization, and high-throughput experimentation, while identifying key areas for future research.
基金supported by the Beijing Natural Science Foundation(Z200011,L233004)the National Key Research and Development Program(2021YFB2500300)+3 种基金the National Natural Science Foundation of China(52394170,52394171,22109011,22393900,and 22108151)the Tsinghua-Jiangyin Innovation Special Fund(TJISF)(2022JYTH0101)the S&T Program of Hebei(22344402D)the Tsinghua University Initiative Scientific Research Program.
文摘All-solid-state lithium batteries(ASSLBs)are strongly considered as the next-generation energy storage devices for their high energy density and intrinsic safety.The solid-solid contact between lithium metal and solid electrolyte plays a vital role in the performance of working ASSLBs,which is challenging to investigate quantitatively by experimental approach.This work proposed a quantitative model based on the finite element method for electrochemical impedance spectroscopy simulation of different solid-solid contact states in ASSLBs.With the assistance of an equivalent circuit model and distribution of relaxation times,it is discovered that as the number of voids and the sharpness of cracks increase,the contact resistance Rcgrows and ultimately dominates the battery impedance.Through accurate fitting,inverse proportional relations between contact resistance Rcand(1-porosity)as well as crack angle was disclosed.This contribution affords a fresh insight into clarifying solid-solid contact states in ASSLBs.
基金financially supported by National Key R&D Program International Cooperation Project(2023YFE0108100)Natural Science Foundation of China(No.52170085)+2 种基金Key Project of Natural Science Foundation of Tianjin(No.21JCZDJC00320)Tianjin Post-graduate Students Research and Innovation Project(2021YJSB013)Fundamental Research Funds for the Central Universities,Nankai University.
文摘Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illustrated the morphological fates of waste leaf-derived graphitic carbon(WLGC)produced from waste ginkgo leaves via pyrolysis temperature regulation and used as bifunctional cathode catalyst for simultaneous H_(2)O_(2) electrochemical generation and organic pollutant degradation,discovering S/N-self-doping shown to facilitate a synergistic effect on reactive oxygen species(ROS)generation.Under the optimum temperature of 800℃,the WLGC exhibited a H_(2)O_(2) selectivity of 94.2%and tetracycline removal of 99.3%within 60 min.Density functional theory calculations and in-situ Fourier transformed infrared spectroscopy verified that graphitic N was the critical site for H_(2)O_(2) generation.While pyridinic N and thiophene S were the main active sites responsible for OH generation,N vacancies were the active sites to produce ^(1)O_(2) from O_(2).The performance of the novel cathode for tetracycline degradation remains well under a wide pH range(3–11),maintaining excellent stability in 10 cycles.It is also industrially applicable,achieving satisfactory performance treating in real water matrices.This system facilitates both radical and non-radical degradation,offering valuable advances in the preparation of cost-effective and sustainable electrocatalysts and hold strong potentials in metal-free EAOPs for organic pollutant degradation.
基金funded by the Israeli Ministry of Innovation,Science and Technology(Grant No.3-11873)the Israel Science Foundation(Grant No.1563/10)+1 种基金the Randy L.and Melvin R.Berlin Family Research Center for Regenerative Medicinethe Gurwin Family Foundation.
文摘Cardiac tissue engineering aims to efficiently replace or repair injured heart tissue using scaffolds,relevant cells,or their combination.While the combination of scaffolds and relevant cells holds the potential to rapidly remuscularize the heart,thereby avoiding the slow process of cell recruitment,the proper ex vivo cellularization of a scaffold poses a substantial challenge.First,proper diffusion of nutrients and oxygen should be provided to the cell-seeded scaffold.Second,to generate a functional tissue construct,cells can benefit from physiological-like conditions.To meet these challenges,we developed a modular bioreactor for the dynamic cellularization of full-thickness cardiac scaffolds under synchronized mechanical and electrical stimuli.In this unique bioreactor system,we designed a cyclic mechanical load that mimics the left ventricle volume inflation,thus achieving a steady stimulus,as well as an electrical stimulus with an action potential profile to mirror the cells’microenvironment and electrical stimuli in the heart.These mechanical and electrical stimuli were synchronized according to cardiac physiology and regulated by constant feedback.When applied to a seeded thick porcine cardiac extracellular matrix(pcECM)scaffold,these stimuli improved the proliferation of mesenchymal stem/stromal cells(MSCs)and induced the formation of a dense tissue-like structure near the scaffold’s surface.Most importantly,after 35 d of cultivation,the MSCs presented the early cardiac progenitor markers Connexin-43 andα-actinin,which were absent in the control cells.Overall,this research developed a new bioreactor system for cellularizing cardiac scaffolds under cardiac-like conditions,aiming to restore a sustainable dynamic living tissue that can bear the essential cardiac excitation–contraction coupling.
基金Material Parts Technology Development Program (20017461, Development and Performance Improvement of Air Operated Valve for 105 MPa Hydrogen Charging Station) funded by the Ministry of Trade,Industry and Energy(MOTIE, Republic of Korea)Korea Evaluation Institute of Industrial Technology (KEIT, Republic of Korea)+1 种基金financial support from the Korea Institute of Energy Technology Evaluation and Planning (KETEP)Ministry of Trade,Industry&Energy (MOTIE) of the Republic of Korea(RS-2024-00419764)。
文摘Lignocellulosic biomass is one of the viable solutions to alleviate the global warming. However, the limited utilization of biomass majorly focused on cellulose and hemicellulose restricts the economic and environmental feasibilities. To cope with this issue, we proposed an integrated process of co-producing 1,6-hexanediol(1,6-HDO) with tetrahydrofuran and adipic acid from biomass, referred to as Strategy A. To compare the impacts of lignin upgrading and feedstock, Strategy B, which co-produces tetrahydrofuran alone, and Strategy C, which is the traditional route to produce 1,6-HDO from fossil fuels, were used. Heat networks are also designed to reduce operating costs and indirect carbon emissions due to energy consumption, saving 87% and 83% of the heat and cooling requirements, respectively, in Strategy A. The market competitiveness of Strategy A was evaluated by determining the minimum selling price through techno-economic analysis, and sustainability was thoroughly investigated by quantifying the environmental impacts through both midpoint and endpoint life-cycle assessments(LCAs).Strategy A was found to be the most favorable both economically(USRDSCHARDOLLAR3,402/ton) and environmentally(-26.9 kg CO_(2)eq.). This indicates that lignin valorization is not only economically but also environmentally preferred. Finally, changes in economic and environmental feasibilities depending on economic, process, and environmental parameters were investigated using sensitivity and uncertainty analyses. The results of these analyses provide valuable insight into bio-based chemical production.
基金the National Natural Science Foundation of China(22279070).
文摘In pursuit of meeting the demands for the next generation of high energy density and flexible electronic products,there is a growing interest in flexible energy storage devices.Silicon(Si)stands out as a promising electrode material due to its high theoretical specific capacity(~3579 mA h g^(-1)),low lithiation potential(~0.40 V),and abundance in nature.We have successfully developed freestanding and flexible CNT/Si/low-melting-point metal(LM)electrodes,which obviate the need for conductive additives,adhesives,and thereby increase the energy density of the device.As an anode material for lithium-ion batteries(LIBs),the CNT/Si/LM electrode demonstrates remarkable cycling stability and rate performance,achieving a reversible capacity of 1871.8 mA h g^(-1)after 100 cycles at a current density of 0.2 A g^(-1).In-situ XRD and in-situ thickness analysis are employed to elucidate the underlying mechanisms during the lithiation/delithiation.Density functional theory(DFT)calculations further substantiate the mechanism by which LM enhances the electrochemical performance of Si,focusing on the aspects of stress mitigation and reduction of the diffusion energy barrier.This research introduces a novel approach to flexible electrode design by integrating CNT films,LM,and Si,thereby charting a path forward for the development of next-generation flexible LIBs.
基金financially supported by the UK Research Council EPRSC EP/W03395X/1the Program grant SynHiSel EP/V047078/1the Hydrogen and Fuel Cells Hub(H_(2)FC SUPERGEN)EP/P024807/1。
文摘Hydrophilicity is critical in Nafion membranes during fuel cell operation as insufficient membrane hydration leads to brittle behavior and a drop in proton conductivity.The incorporation of APTS(3-(aminopro pyl)triethoxysilane)into exfoliated graphene oxide(EGO)by covalent functionalization to be used as filler into Nafion membranes allows higher hydrophilicity for these membranes.This is associated with promoting hydroxyl,carbonyl,siloxane,silane,and amine groups within the EGO-APTS matrix.The incorporation of these materials as Fuel Cell MEAs leads to a significant reduction of the ohmic resistance measured at high frequency resistance(HFR)in electrochemical impedance spectroscopy(EIS)experiments and achieves maximum power densities of 1.33 W cm^(-2)at 60℃ at 100%RH(APTS-EGO,0.2 wt%)and1.33 W cm^(-2)at 60℃ at 70%RH(APTS-EGO,0.3 wt%),which represents an improvement of 190%compared to the commercial Nafion 212 when utilizing low humidification conditions(70%).Moreover,the as-synthesized membrane utilizes lower Nafion ionomer mass,which,in conjunction with the excellent cell performance,has the potential to decrease the cost of the membrane from 87 to 80￡/W as well as a reduction of fluorinated compounds within the membrane.
基金financial support from the National Natural Science Foundation of China(No.22379001 and 22309003)the Natural Science Research Project of Anhui Province Education department(No.2022AH030046)the Top Young Talents of Anhui University of Technology,the Young Scholars of the Introduction and Education of Talents in Anhui Province,and the Scientific Research Foundation of Anhui University of Technology for Talent Introduction。
文摘Metal-sulfur electrochemistry represents a promising energy storage technology due to the natural abundance and unparalleled theoretical specific capacity of 1675 mAh g^(-1)of sulfur based on two-electron redox reaction(S^(0)■S^(2-)).Commercially viable metal-sulfur batteries(MSBs)are hindered by sluggish sulfur conversion kinetics,which reduce the utilization efficiency of sulfur and lead to polysulfide shuttling.Single-atom catalysts(SACs)exhibit specific catalytic activity,a high atomic utilization ratio,and flexible selectivity,and are considered exceptional electrocatalysts for addressing the intractable challenges encountered by the MSBs.This review summarizes the recent progress in SACs for boosting the sulfur electrochemistry in MSBs,focusing on sulfur host materials,modified separators and functional interlayers,and analyzes the in-depth mechanisms of SACs.Moreover,the correlation between the coordination environments and the intrinsic activity of SACs is discussed.Finally,the main challenges and potential research directions of SACs for high-energy-density and long-life MSBs are outlined.This study provides significant guidance for constructing novel SACs that can accelerate the sulfur conversion kinetics in MSBs.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.RS-2024-00453815)Korea Institute of Energy Technology Evaluation and Planning(KETEP)grant funded by the Korea government(MOTIE)(20228510070100)。
文摘Recently,potassium-ion batteries(PIBs)have received significant attention in the energy storage field owing to their high-power output,fast charging capability,natural abundance,and environmental sustainability.Herein,we comprehensively review recent advancements in the design and development of carbon-based anode materials for PIBs anodes,covering graphite,hard carbon,alloy and conversion materials with carbon,and carbon host for K metal deposition.Chemical strategies such as structural engineering,heteroatom-doping,and surface modifications are highlighted to improve electrochemical performances as well as to resolve technical challenges,such as electrode instability,low initial Coulombic efficiency,and electrolyte compatibility.Furthermore,we discuss the fundamental understanding of potassium-ion storage mechanisms of carbon-based materials and their correlation with electrochemical performance.Finally,we present the current challenges and future research directions for the practical implementation of carbon-based anodes to enhance their potential as next-generation energy storage materials for PIBs.This review aims to provide our own insights into innovative design strategies for advanced PIB's anode through the chemical and engineering strategies.
基金supported by Henan Province Key Research and Development and Promotion of Science and Technology Project(No.25A150001)the National Natural Science Foundation of China(Nos.22409171,22125303,92361302,and 92061203).
文摘Single-atom catalysts(SACs),as the rising stars in the field of catalytic science,are leading catalytic technology into an un-precedented new era.However,the synthe-sis of high-performance SACs with well-de-fined active sites and high loadings under precise control has become a hotly debated topic in scientific research.Metal-organic frameworks(MOFs),with their exceptional properties such as ultrahigh specific surface areas,precisely controllable structural de-signs,and highly flexible functional cus-tomization capabilities,are regarded as one of the ideal matrices for supporting and sta-bilizing SACs.This review provides an in-sightful overview of the diverse preparation strategies for MOFs-derived SACs.It comprehen-sively analyzes the unique advantages and challenges of each method in achieving efficient synthesis of SACs,emphasizing the crucial role of optimized processes in unlocking the antici-pated performance of SACs.Furthermore,this review delves into a series of advanced charac-terization techniques,including aberration-corrected scanning transmission electron mi-croscopy(AC-STEM),electron energy loss spectroscopy(EELS),X-ray absorption spec-troscopy(XAS),and infrared absorption spectroscopy(IRAS),offering valuable insights into the atomic-scale fine structures and properties of SACs,significantly advancing the under-standing of SAC mechanisms.Moreover,this review focuses on exploring the potential appli-cations of MOFs-derived SACs in electrocatalysis frontier fields.This comprehensive exami-nation lays a solid theoretical foundation and provides a directional guidance for the rational design and controllable synthesis of high-performance MOFs-derived SACs.
基金funded by the National Research Foundation(NRF)of Korea(2020M3H4A3081816,RS-2023-00304936,and RS-2024-00398065).
文摘Various novel conjugated polymers(CPs)have been developed for organic photodetectors(OPDs),but their application to practical image sensors such as X-ray,R/G/B,and fingerprint sensors is rare.In this article,we report the entire process from the synthesis and molecular engineering of novel CPs to the development of OPDs and fingerprint image sensors.We synthesized six benzo[1,2-d:4,5-d’]bis(oxazole)(BBO)-based CPs by modifying the alkyl side chains of the CPs.Several relationships between the molecular structure and the OPD performance were revealed,and increasing the number of linear octyl side chains on the conjugated backbone was the best way to improve Jph and reduce Jd in the OPDs.The optimized CP demonstrated promising OPD performance with a responsivity(R)of 0.22 A/W,specific detectivity(D^(*))of 1.05×10^(13)Jones at a bias of-1 V,rising/falling response time of 2.9/6.9μs,and cut-off frequency(f_(-3dB))of 134 kHz under collimated 530 nm LED irradiation.Finally,a fingerprint image sensor was fabricated by stacking the POTB1-based OPD layer on the organic thin-film transistors(318 ppi).The image contrast caused by the valleys and ridges in the fingerprints was obtained as a digital signal.
基金financial support from the National Natural Science Foundation of China[grant number 21878299]。
文摘Polymer binders possess significant potential in alleviating the volume expansion issues of silicon-based anodes,yet remain challenging due to insufficient interfacial interactions with individual components(Si,C,and Cu)of the anode.Herein,we report the synthesis of a stable three-dimensional network structure of the PAA-PEA(polyacrylic acid-polyether amines)polymer binder through intermolecular physicochemical dual cross-linking.By incorporating polar functional groups,the binder molecules not only form strong C-O-Si,N-Si,O=C-O-C,and O=C-O-Cu covalent bonds but also enhance non-covalent interactions with Si,C,and Cu,thereby improving adhesion between the binder and each interface of the anode.Furthermore,weak hydrogen bonds,acting as"sacrificial bonds",dissipate energy and disperse accumulated stress,improving the material flexibility.Due to the high mechanical stability of the framework,which combines both rigidity and flexibility and the coupling effect at the three interfaces,the movement and separation of electrode components are effectively restrained,significantly enhancing the cycling stability of silicon-graphite anodes.The PAA-PEA 2000 electrode exhibits a capacity retention of 78% after 500 cycles at a current density of 0.2 A g^(-1).This work provides insights into the mechanism of binders and guides the design of polymer binders for high-performance Si-based electrodes.
基金supported by the National Natural Science Foundation of China(22378126)National Key Research and Development Program of the International scientific and technological innovation cooperation project among governments(2021YFE0100400)Shanghai Science and Technology Innovation Action Plan(22501100500).
文摘Integrating multiple modalities of cancer therapies for synergistic and enhanced therapeutic efficacy remains challenging.Herein,flash nanoprecipitation(FNP),a kinetically driven process,was employed to expedite the coordination reaction time required for nano-encapsulate components with completely opposite physiochemical properties including sorafenib(SRF),hemoglobin(Hb),chlorin e6(Ce6),and indocyanine green(ICG)into a multi-component HSCI nanomedicine.Hydrophilic components Hb and ICG interact to form hydrophobic ICG-Hb complexes under electrostatic and hydrophobic interactions.This process facilitates the characteristic time of nucleation(τ_(nucleation))to match the characteristic mixing time(τ_(mix))of the FNP process,resulting in the formulation of kinetically stable nanomedicine,overcoming the long equilibrium times and instability issues associated with thermodynamic assembly.Importantly,pH-responsive structure is also easily but effectively integrated in nanomedicine during this kinetically driven formulation to manipulate its structures.In the acidic tumor microenvironment(TME),the pH-stimulated morphology transformation of HSCI nanomedicine boosts its reactive oxygen species(ROS)generation efficiency and photothermal efficacy,endowing it with better antitumor suppression.In vitro and in vivo experiments reveal that the HSCI nanomedicine offers a synergistic therapeutic effect and stronger tumor suppression compared with single therapies.These results open a new window for developing strategies for multimodal combinatory cancer therapies.
基金supported as part of The Center for LignoCellulose Structure and Formation,an Energy Frontier Research Center funded by the U.S.Department of Energy,Office of Science,Basic Energy Sciences under Award#DE-SC0001090support from the Huck Institutes of the Life Sciences at Penn State University through the Patricia and Stephen Benkovic Research Initiativesupported by the Center for Engineering Mechano Biology(CEMB),an NSF Science and Technology Center,under grant agreement CMMI:15-48571。
文摘Plant cell wall(CW)-like soft materials,referred to as artificial CWs,are composites of assembled polymers containing micro-/nanoparticles or fibers/fibrils that are designed to mimic the composition,structure,and mechanics of plant CWs.CW-like materials have recently emerged to test hypotheses pertaining to the intricate structure–property relationships of native plant CWs or to fabricate functional materials.Here,research on plant CWs and CW-like materials is reviewed by distilling key studies on biomimetic composites primarily composed of plant polysaccharides,including cellulose,pectin,and hemicellulose,as well as organic polymers like lignin.Micro-and nanofabrication of plant CW-like composites,characterization techniques,and in silico studies are reviewed,with a brief overview of current and potential applications.Micro-/nanofabrication approaches include bacterial growth and impregnation,layer-by-layer assembly,film casting,3-dimensional templating microcapsules,and particle coating.Various characterization techniques are necessary for the comprehensive mechanical,chemical,morphological,and structural analyses of plant CWs and CW-like materials.CW-like materials demonstrate versatility in real-life applications,including biomass conversion,pulp and paper,food science,construction,catalysis,and reaction engineering.This review seeks to facilitate the rational design and thorough characterization of plant CW-mimetic materials,with the goal of advancing the development of innovative soft materials and elucidating the complex structure–property relationships inherent in native CWs.
文摘Magnesium(Mg)-based bioresorbable stents represent a potentially groundbreaking advancement in cardiovascular therapy;offering tem-porary vessel support and complete biodegradability—addressing limitations of traditional stents like in-stent restenosis and long-term com-plications.However,challenges such as rapid corrosion and suboptimal endothelialisation have hindered their clinical adoption.This review highlights the latest breakthroughs in surface modification,alloying,and coating strategies to enhance the mechanical integrity,corrosion resistance,and biocompatibility of Mg-based stents.Key surface engineering techniques,including polymer and bioactive coatings,are ex-amined for their role in promoting endothelial healing and minimising inflammatory responses.Future directions are proposed,focusing on personalised stent designs to optimize efficacy and long-term outcomes,positioning Mg-based stents as a transformative solution in interventional cardiology.
基金financially supported by the National Natural Science Foundation of China(22378227)the National Research Foundation,Singapore,and A*STAR under its Low-Carbon Energy Research(LCER)Funding Initiative(FI)Project(U2102d2011,WBS:A-8000278-00-00)the Medium Energy X-ray Absorption Spectroscopy beamline at the Australian Synchrotron,part of ANSTO。
文摘Dry reforming of methane(DRM)over Ni-based catalysts is an economically reasonable technology for large-scale CO_(2)utilization.However,prolonged Ni sintering and carbon deposition reduce the durability and efficiency of DRM,hindering its engineering application.Herein,we propose a facile approach by combining continuous microscale coprecipitation with solid-state reactions to construct a BaAl_(2)O_(4)-overlayer-confined Ni catalyst.The 5-wt%-Ni@BaAl_(2)O_(4)catalyst exhibited advanced CO_(2)and CH_(4)conversions of 96% and 86% at 800℃ and a GHSV of 144 L g_(cat)^(-1).h^(-1).Moreover,the k_(d)-CO_(2)and k_(d)-CH_(4)of Ni@BaAl_(2)O_(4)were 0.0063 and 0.0029 h^(-1);which are approximately half and one-thirds of those of Ni/BaAl_(2)O_(4)and slightly better than those of Ni@MgAl_(2)O_(4),underscoring the versatility of the proposed synthesis protocol for constructing core-shell structures.XAS,HAADF-STEM-EDS,and CO transmission-IR characterizations confirmed the SMSI of~2-nm amorphous BaAl_(2)O_(4)-overlaid~10 nm Ni with an overall mesoporous structure.After a long-term test,the sintering and coking inhibition effects of Ni@BaAl_(2)O_(4)(10→11 nm,0.55 mgCg_(cat)^(-1).h^(-1))outperformed Ni/BaAl_(2)O_(4)(13→22 nm,1.90 mgCg_(cat)^(-1).h^(-1))and Ni@MgAl_(2)O_(4).In situ time-resolved CH4→CO_(2)transient response,DRIFTS experiments,and DFT calculations suggested that Ni@BaAl_(2)O_(4)and Ni/BaAl_(2)O_(4)followed the Mars-van Krevelen and Langmuir-Hinshelwood redox mechanisms,respectively.The functional interfacial lattice oxygen promoted the removal of C_(ads)^(*)on Ni and core-shell structure induced fast CO_(2)adsorption and CO desorption.The present study provides a facile approach for constructing a stable and active Ni-based core-shell catalyst.Furthermore,it offers novel insights into the functionalities of non-reducible spinel overlayers in the DRM process.
文摘CO_(2) hydrogenation to CH3OH is of great significance for achieving carbon neutrality.Here,we show a urea-assisted grinding strategy for synthesizing Cu-Zn-Ce ternary catalysts(CZC-G)with optimized interfacial synergy,achieving superior performance in CO_(2) hydrogenation to methanol.The CZC-G catalyst demonstrated exceptional methanol selectivity(96.8%)and a space-time yield of 73.6 gMeOH·kgcat^(–1)·h^(–1) under optimized conditions.Long-term stability tests confirmed no obvious deactivation over 100 h of continuous operation.Structural and mechanistic analyses revealed that the urea-assisted grinding method promotes the formation of Cu/Zn-O_(v)-Ce ternary interfaces and inhibits the reduction of ZnO,enabling synergistic interactions for efficient CO_(2) activation and selective stabilization of formate intermediates(HCOO^(*)),which are critical for methanol synthesis.In-situ diffuse reflectance infrared Fourier transform spectra and X-ray absorption spectroscopy studies elucidated the reaction pathway dominated by the formate mechanism,while suppressing the reverse water-gas shift reaction.This work underscores the critical role of synthetic methodologies in engineering interfacial structures,offering a strategy for designing high-performance catalysts for sustainable CO_(2) resource utilization.
基金the financial support from the Science, Technology, and Innovation Funding Authority (STIFA, STDF previously) through project number 42691 entitled “Microstructure-Based, Multi-Physics Simulation and Optimization to Improve Battery Performance”supported by the U.S. DOE (Department of Energy), Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357supported by the U.S. DOE Vehicle Technologies office, under contract number DE-AC02-06CH11357
文摘This study investigates the electrochemical behavior of molybdenum disulfide(MoS_(2))as an anode in Li-ion batteries,focusing on the extra capacity phenomenon.Employing advanced characterization methods such as in situ and ex situ X-ray diffraction,Raman spectroscopy,X-ray photoelectron spectroscopy,and transmission electron microscopy,the research unravels the complex structural and chemical evolution of MoS_(2) throughout its cycling.A key discovery is the identification of a unique Li intercalation mechanism in MoS_(2),leading to the formation of reversible Li_(2)MoS_(2) phases that contribute to the extra capacity of the MoS_(2) electrode.Density function theory calculations suggest the potential for overlithiation in MoS_(2),predicting Li5MoS_(2) as the most energetically favorable phase within the lithiation–delithiation process.Additionally,the formation of a Li-rich phase on the surface of Li_(4)MoS_(2) is considered energetically advantageous.After the first discharge,the battery system engages in two main reactions.One involves operation as a Li-sulfur battery within the carbonate electrolyte,and the other is the reversible intercalation and deintercalation of Li in Li_(2)MoS_(2).The latter reaction contributes to the extra capacity of the battery.The incorporation of reduced graphene oxide as a conductive additive in MoS_(2) electrodes notably improves their rate capability and cycling stability.
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.
文摘This paper discussed an extended model for flexibility analysis of chemical process. Under uncertainty, probability density function is used to describe uncertain parameters instead of hyper-rectangle, and chanceconstrained programming is a feasible way to deal with the violation of constraints. Because the feasible region of control variables would change along with uncertain parameters, its smallest acceptable size threshold is presented to ensure the controllability condition. By synthesizing the considerations mentioned above, a modified model can describe the flexibility analysis problem more exactly. Then a hybrid algorithm, which integrates stochastic simulation and genetic algorithm, is applied to solve this model and maximize the flexibility region. Both numerical and chemical process examples are presented to demonstrate the effectiveness of the method.
