Electrocatalytic urea synthesis provides a favorable strategy for conventional energy-consuming urea synthesis,but achieving large-scale catalyst synthesis with high catalytic efficiency remains challenging.Herein,we ...Electrocatalytic urea synthesis provides a favorable strategy for conventional energy-consuming urea synthesis,but achieving large-scale catalyst synthesis with high catalytic efficiency remains challenging.Herein,we developed a simple method for the preparation of a series of FeNi-alloy-based catalysts,named FeNi@nC-T(n represents the content of nanoporous carbon as 1,3,5,7 or 9 g and T=900,950,1000 or 1100°C),for highly performed urea synthesis via NO_(3)−and CO_(2)co-reduction.The FeNi@7C-1000 achieved a high urea yield of 1041.33 mmol h^(−1)gFeNi^(−1)with a Faradaic efficiency of 15.56%at–1.2 V vs.RHE.Moreover,the scale-up synthesized FeNi@7C-950-S(over 140 g per batch)was achieved with its high catalytic performance and high stability maintained.Mechanism investigation illuminated that the Ni and Fe sites catalyze and stabilize the key*CO and*N intermediates and minimize the C–N coupling reaction barriers for highly efficient urea synthesis.展开更多
Research on the synthesis of superoxide dismutase mimics by chemical and biologi-cal synthetic methods were reviewed.The advantages and limitations were analyzed.A prospect for the future development of superoxide dis...Research on the synthesis of superoxide dismutase mimics by chemical and biologi-cal synthetic methods were reviewed.The advantages and limitations were analyzed.A prospect for the future development of superoxide dismutase mimics is proposed.展开更多
Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts...Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.展开更多
Zeolites have been widely used as catalysts,ion-exchangers,and adsorbents in chemical industries,detergent industry,steel industry,glass industry,ceramic industry,medical and healthfield,and environmentalfield,and recen...Zeolites have been widely used as catalysts,ion-exchangers,and adsorbents in chemical industries,detergent industry,steel industry,glass industry,ceramic industry,medical and healthfield,and environmentalfield,and recently applied in energy storage.Seed-assisted synthesis is a very effective approach in promoting the crystallization of zeolites.In some cases,the target zeolite cannot be formed in the absence of seed zeolite.In homologous seed-assisted synthesis,the structure of the seed zeolite is the same to that of the target zeolite,while the structure of the seed zeolite is different to that of the target zeolite in the heterologous seed-assisted synthesis.In this review,we briefly summarized the heterologous seed-assisted syntheses of zeolites and analyzed the structure-directing effect of heterologous seeds and surveyed the“common composite building units(CBUs)hypothesis”and the“common secondary building units(SBUs)hypothesis”.However,both hypotheses cannot explain all observations on the heterologous seed-assisted syntheses.Finally,we proposed that the formation of the target zeolite does need nuclei with the structure of target zeolite and the formation of the nuclei of the target zeolite can be promoted by either the undissolved seed crystals with the same CBUs or SBUs to the target zeolite or by the facilitated appropriate distribution of the specific building units due to the presence of the heterologous seed that does not have any common CBUs and SBUs with the target zeolite.展开更多
Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficien...Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.展开更多
In the realm of the synthesis of heat-integrated distillation configurations,the conventional approach for exploring more heat integration possibilities typically entails the splitting of a single column into a twocol...In the realm of the synthesis of heat-integrated distillation configurations,the conventional approach for exploring more heat integration possibilities typically entails the splitting of a single column into a twocolumn configuration.However,this approach frequently necessitates tedious enumeration procedures,resulting in a considerable computational burden.To surmount this formidable challenge,the present study introduces an innovative remedy:The proposition of a superstructure that encompasses both single-column and multiple two-column configurations.Additionally,a simultaneous optimization algorithm is applied to optimize both the process parameters and heat integration structures of the twocolumn configurations.The effectiveness of this approach is demonstrated through a case study focusing on industrial organosilicon separation.The results underscore that the superstructure methodology not only substantially mitigates computational time compared to exhaustive enumeration but also furnishes solutions that exhibit comparable performance.展开更多
In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterpart...In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.展开更多
Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high...Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.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
Free amino acid(FAA)is the important component of vinegar that infl uences quality perception and consumer acceptance.FAA is one of the major metabolites produced by microorganisms;however,the microbial metabolic netw...Free amino acid(FAA)is the important component of vinegar that infl uences quality perception and consumer acceptance.FAA is one of the major metabolites produced by microorganisms;however,the microbial metabolic network on FAA biosynthesis remains unclear.Through metagenomic analysis,this work aimed to elucidate the roles of microbes in FAA biosynthesis during Monascus rice vinegar fermentation.Taxonomic profiles from functional analyses showed 14 dominant genera with high contributions to the metabolism pathways.The metabolic network for FAA biosynthesis was then constructed,and the microbial distribution in different metabolic pathways was illuminated.The results revealed that 5 functional genera were closely involved in FAA biosynthesis.This study illuminated the metabolic roles of microorganisms in FAA biosynthesis and provided crucial insights into the functional attributes of microbiota in vinegar fermentation.展开更多
Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such ...Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.展开更多
Developing a simple scalable method to fabricate electrodes with high capacity and wide voltage range is desired for the real use of electrochemical supercapacitors.Herein,we synthesized amorphous NiCo-LDH nanosheets ...Developing a simple scalable method to fabricate electrodes with high capacity and wide voltage range is desired for the real use of electrochemical supercapacitors.Herein,we synthesized amorphous NiCo-LDH nanosheets vertically aligned on activated carbon cloth substrate,which was in situ transformed from Co-metal-organic framework materials nano-columns by a simple ion exchange process at room temperature.Due to the amorphous and vertically aligned ultrathin structure of NiCo-LDH,the NiCo-LDH/activated carbon cloth composites present high areal capacities of 3770 and 1480 mF cm^(-2)as cathode and anode at 2 mA cm^(-2),and 79.5%and 80%capacity have been preserved at 50 mA cm^(-2).In the meantime,they all showed excellent cycling performance with negligible change after>10000 cycles.By fabricating them into an asymmetric supercapacitor,the device achieves high energy densities(5.61 mWh cm^(-2)and 0.352 mW cm^(-3)).This work provides an innovative strategy for simplifying the design of supercapacitors as well as providing a new understanding of improving the rate capabilities/cycling stability of NiCo-LDH materials.展开更多
Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sit...Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.展开更多
The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia syn...The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia synthesis.While the process is thermodynamically feasible at ambient temperature and pressure,challenges such as the competing hydrogen evolution reaction,low nitrogen solubility in electrolytes,and the activation of inert dinitrogen(N_(2))gas adversely affect the performance of ammonia production.These hurdles result in low Faradaic efficiency and low ammonia production rate,which pose obstacles to the commercialisation of the process.Researchers have been actively designing and proposing various electrocatalysts to address these issues,but challenges still need to be resolved.A key strategy in electrocatalyst design lies in understanding the underlying mechanisms that govern the success or failure of the electrocatalyst in driving the electrochemical reaction.Through mechanistic studies,we gain valuable insights into the factors affecting the reaction,enabling us to propose optimised designs to overcome the barriers.This review aims to provide a comprehensive understanding of the various mechanisms involved in eNRR on the electrocatalyst surface.It delves into the various mechanisms such as dissociative,associative,Mars-van Krevelen,lithium-mediated nitrogen reduction and surface hydrogenation mechanisms of nitrogen reduction.By unravelling the intricacies of eNRR mechanisms and exploring promising avenues,we can pave the way for more efficient and commercially viable ammonia synthesis through this sustainable electrochemical process by designing an efficient electrocatalyst.展开更多
In order to improve the energy output consistency of 3, 3’-diamino-4, 4’-azoxyfurazan(DAAF) in the new insensitive booster and the safety and efficiency in the preparation process, a continuous preparation system of...In order to improve the energy output consistency of 3, 3’-diamino-4, 4’-azoxyfurazan(DAAF) in the new insensitive booster and the safety and efficiency in the preparation process, a continuous preparation system of DAAF from synthesis to spherical coating was designed and established in this paper, which combined ultrasonic micromixing reaction with microdroplet globular template. In the rapid micromixing stage, the microfluidic mixing technology with ultrasonic was used to synergistically strengthen the uniform and rapid mass transfer mixing reaction between raw materials to ensure the uniformity of DAAF particle nucleation-growth, and to prepare high-quality DAAF crystals with uniform structure and morphology and concentrated particle size distribution. In the microdroplet globular template stage, the microfluidic droplet technology was used to form a droplet globular template with uniform size under the shear action of the continuous phase of the dispersed phase solution containing DAAF particles and binder. The size of the droplet template was controlled by adjusting the flow rate ratio between the continuous phase and the dispersed phase. In the droplet globular template, with the diffusion of the solvent in the dispersed phase droplets, the binder precipitates to coat the DAAF into a ball, forming a DAAF microsphere with high sphericity, narrow particle size distribution and good monodispersity. The problem of discontinuity and DAAF particle suspension in the process was solved, and the coating theory under this process was studied. DAAF was coated with different binder formulations of fluororubber(F2604), nitrocellulose(NC) and NC/glycidyl azide polymer(GAP), and the process verification and evaluation of the system were carried out. The balling effects of large, medium and small droplet templates under different binder formulations were studied. The scanning electron microscope(SEM) results show that the three droplet templates under the three binder formulations exhibit good balling effect and narrow particle size distribution. The DAAF microspheres were characterized by powder X-ray diffraction(XRD), differential scanning calorimetry(DSC), thermo-gravimetric(TG) and sensitivity analyzer. The results showed that the crystal structure of DAAF did not change during the process, and the prepared DAAF microspheres had lower decomposition temperature and lower mechanical sensitivity than raw DAAF. The results of detonation parameters show that the coating of DAAF by using the above three binder formulations will not greatly reduce the energy output of DAAF, and has comparable detonation performance to raw DAAF. This study proves an efficient and safe continuous system from synthesis to spherical coating modification of explosives, which provides a new way for the continuous, safe and efficient preparation of spherical explosives.展开更多
The coal-to-ethanol process,as the clean coal utilization,faces challenges from the energy-intensive distillation that separates multi-component effluents for pure ethanol.Referring to at least eight columns,the synth...The coal-to-ethanol process,as the clean coal utilization,faces challenges from the energy-intensive distillation that separates multi-component effluents for pure ethanol.Referring to at least eight columns,the synthesis of the ethanol distillation system is impracticable for exhaustive comparison and difficult for conventional superstructure-based optimization as rigorous models are used.This work adopts a superstructure-based framework,which combines the strategy that adaptively selects branches of the state-equipment network and the parallel stochastic algorithm for process synthesis.High-performance computing significantly reduces time consumption,and the adaptive strategy substantially lowers the complexity of the superstructure model.Moreover,parallel computing,elite search,population redistribution,and retention strategies for irrelevant parameters are used to improve the optimization efficiency further.The optimization terminates after 3000 generations,providing a flowsheet solution that applies two non-sharp splitting options in its distillation sequence.As a result,the 59-dimension superstructure-based optimization was solved efficiently via a differential evolution algorithm,and a high-quality solution with a 28.34%lower total annual cost than the benchmark was obtained.Meanwhile,the solution of the superstructure-based optimization is comparable to that obtained by optimizing a single specific configuration one by one.It indicates that the superstructure-based optimization that combines the adaptive strategy can be a promising approach to handling the process synthesis of large-scale and complex chemical processes.展开更多
Oxynitride semiconductors are promising photocatalyst materials for visible light-driven water splitting,while the synthesis of well crystalized oxynitride still remains challenge.In present work,narrow-bandgap TaON n...Oxynitride semiconductors are promising photocatalyst materials for visible light-driven water splitting,while the synthesis of well crystalized oxynitride still remains challenge.In present work,narrow-bandgap TaON nanoparticles are synthesized via heating a vacuum-sealed mixture of KTaO_(3),Ta and NH_(4)Cl.This method possesses multiple advantages in terms of lower calcination parameter,higher N conversion efficiency and superior photocatalytic activity in comparison with the traditional thermal ammonolysis using NH_(3) gas as a nitrogen source.Through the analysis of intermediates produced upon the elevation of heating temperature,a gas-solid-phase reaction between TaCl_(5) and Ta_(2)O_(5) is demonstrated as the final step,which is conducive to decreasing thermal energy barrier and accelerating nitridation process.Precise control of preparation conditions,including calcination temperature and duration,allows for the regulation of surface O/N ratio of TaON particles to unity,resulting in optimized photocat-alytic activity.Photoelectrochemical assessment and intensity modulated photocurrent spectroscopy provide convincing evidence for improved charge transfer effciency of photoexcited holes at TaON surface.A Z-scheme overall water splitting is accomplished by employing the TaON as an effective oxygen evolution photocatalyst,SrTiO_(3):Rh as a hydrogen evolution photocatalyst,and reduced graphene oxide(rGO)as a solid-state electron mediator.This work presents a promising strategy for the synthesis of high-quality oxynitride materials in application to photocatalytic water splitting.展开更多
The current parallel ankle rehabilitation robot(ARR)suffers from the problem of difficult real-time alignment of the human-robot joint center of rotation,which may lead to secondary injuries to the patient.This study ...The current parallel ankle rehabilitation robot(ARR)suffers from the problem of difficult real-time alignment of the human-robot joint center of rotation,which may lead to secondary injuries to the patient.This study investigates type synthesis of a parallel self-alignment ankle rehabilitation robot(PSAARR)based on the kinematic characteristics of ankle joint rotation center drift from the perspective of introducing"suitable passive degrees of freedom(DOF)"with a suitable number and form.First,the self-alignment principle of parallel ARR was proposed by deriving conditions for transforming a human-robot closed chain(HRCC)formed by an ARR and human body into a kinematic suitable constrained system and introducing conditions of"decoupled"and"less limb".Second,the relationship between the self-alignment principle and actuation wrenches(twists)of PSAARR was analyzed with the velocity Jacobian matrix as a"bridge".Subsequently,the type synthesis conditions of PSAARR were proposed.Third,a PSAARR synthesis method was proposed based on the screw theory and type of PSAARR synthesis conducted.Finally,an HRCC kinematic model was established to verify the self-alignment capability of the PSAARR.In this study,93 types of PSAARR limb structures were synthesized and the self-alignment capability of a human-robot joint axis was verified through kinematic analysis,which provides a theoretical basis for the design of such an ARR.展开更多
MXene has been the limelight for studies on electrode active materials,aiming at developing supercapacitors with boosted energy density to meet the emerging influx of wearable and portable electronic devices.Despite i...MXene has been the limelight for studies on electrode active materials,aiming at developing supercapacitors with boosted energy density to meet the emerging influx of wearable and portable electronic devices.Despite its various desirable properties including intrinsic flexibility,high specific surface area,excellent metallic conductivity and unique abundance of surface functionalities,its full potential for electrochemical performance is hindered by the notorious restacking phenomenon of MXene nanosheets.Ascribed to its two-dimensional(2D)nature and surface functional groups,inevitable Van der Waals interactions drive the agglomeration of nanosheets,ultimately reducing the exposure of electrochemically active sites to the electrolyte,as well as severely lengthening electrolyte ion transport pathways.As a result,energy and power density deteriorate,limiting the application versatility of MXene-based supercapacitors.Constructing 3D architectures using 2D nanosheets presents as a straightforward yet ingenious approach to mitigate the fatal flaws of MXene.However,the sheer number of distinct methodologies reported,thus far,calls for a systematic review that unravels the rationale behind such 3D MXene structural designs.Herein,this review aims to serve this purpose while also scrutinizing the structure–property relationship to correlate such structural modifications to their ensuing electrochemical performance enhancements.Besides,the physicochemical properties of MXene play fundamental roles in determining the effective charge storage capabilities of 3D MXene-based electrodes.This largely depends on different MXene synthesis techniques and synthesis condition variations,hence,elucidated in this review as well.Lastly,the challenges and perspectives for achieving viable commercialization of MXene-based supercapacitor electrodes are highlighted.展开更多
High alumina fly ash(FAHAl)is a kind of bulk solid waste unique to China,whose availability of high-value aluminum and the threat to the environment makes its high-value utilization urgent.In this work,the alumina con...High alumina fly ash(FAHAl)is a kind of bulk solid waste unique to China,whose availability of high-value aluminum and the threat to the environment makes its high-value utilization urgent.In this work,the alumina containing leaching solution obtained from Na_(2)CO_(3) roasting and HCl leaching of FAHAl was used as the mother liquor to prepare layered boehmite in situ.The preparation process with AlCl_(3) as the raw material was also compared.The formation process and mechanism of boehmite,the choice of solvent,along with the adsorption capability of Congo red were analyzed by X-ray diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,Brunauer-Emmett-Teller method and adsorption experiments.Results showed that during the preparation of layered boehmite,the precursor Al(OH)_(3) from the reaction of Al^(3+) and OH-is transformed into boehmiteγ-AlOOH.The existence of ethanol is beneficial to regulate and promote the growth of boehmite crystal effectively.When water and ethanol are mixed with a volume ratio of 2:1 and used as the solvent,the maximum specific surface area of the boehmite is obtained at 135.7 m^(2)·g^(-1),and 99.16%of Congo red can be absorbed after 10 min when AlCl3 is used as a raw material.As purified leaching solution is used as the mother liquid,the crystallinity of boehmite decreases slightly when the pH value decreases from 12.5 to 11.When pH is 11,the removal efficiency of Congo red reaches a maximum of 72.25%.This process not only achieves the extraction of aluminum and high-value utilization of FAHAl but also provides a thought to prepare layered boehmite with adsorption properties.展开更多
文摘Electrocatalytic urea synthesis provides a favorable strategy for conventional energy-consuming urea synthesis,but achieving large-scale catalyst synthesis with high catalytic efficiency remains challenging.Herein,we developed a simple method for the preparation of a series of FeNi-alloy-based catalysts,named FeNi@nC-T(n represents the content of nanoporous carbon as 1,3,5,7 or 9 g and T=900,950,1000 or 1100°C),for highly performed urea synthesis via NO_(3)−and CO_(2)co-reduction.The FeNi@7C-1000 achieved a high urea yield of 1041.33 mmol h^(−1)gFeNi^(−1)with a Faradaic efficiency of 15.56%at–1.2 V vs.RHE.Moreover,the scale-up synthesized FeNi@7C-950-S(over 140 g per batch)was achieved with its high catalytic performance and high stability maintained.Mechanism investigation illuminated that the Ni and Fe sites catalyze and stabilize the key*CO and*N intermediates and minimize the C–N coupling reaction barriers for highly efficient urea synthesis.
文摘Research on the synthesis of superoxide dismutase mimics by chemical and biologi-cal synthetic methods were reviewed.The advantages and limitations were analyzed.A prospect for the future development of superoxide dismutase mimics is proposed.
基金the support from the CIPHER Project(IIID 2018-008)funded by the Commission on Higher Education-Philippine California Advanced Research Institutes(CHED-PCARI)。
文摘Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.
基金support from the National Key Research and Development Program of China(2021YFA1500401,2021YFA1501202)the National Natural Science Foundation of China(22288101)the 111 Project(B17020)for supporting this work.
文摘Zeolites have been widely used as catalysts,ion-exchangers,and adsorbents in chemical industries,detergent industry,steel industry,glass industry,ceramic industry,medical and healthfield,and environmentalfield,and recently applied in energy storage.Seed-assisted synthesis is a very effective approach in promoting the crystallization of zeolites.In some cases,the target zeolite cannot be formed in the absence of seed zeolite.In homologous seed-assisted synthesis,the structure of the seed zeolite is the same to that of the target zeolite,while the structure of the seed zeolite is different to that of the target zeolite in the heterologous seed-assisted synthesis.In this review,we briefly summarized the heterologous seed-assisted syntheses of zeolites and analyzed the structure-directing effect of heterologous seeds and surveyed the“common composite building units(CBUs)hypothesis”and the“common secondary building units(SBUs)hypothesis”.However,both hypotheses cannot explain all observations on the heterologous seed-assisted syntheses.Finally,we proposed that the formation of the target zeolite does need nuclei with the structure of target zeolite and the formation of the nuclei of the target zeolite can be promoted by either the undissolved seed crystals with the same CBUs or SBUs to the target zeolite or by the facilitated appropriate distribution of the specific building units due to the presence of the heterologous seed that does not have any common CBUs and SBUs with the target zeolite.
基金The financial supports from the National Natural Science Foundation of China (22178059, 22208054 and 22072019)Natural Science Foundation of Fujian Province, China (2020J01513)+1 种基金Sinochem Quanzhou Energy Technology Co., Ltd. (ZHQZKJ-19-F-ZS0076)Qingyuan Innovation Laboratory (00121002)
文摘Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.
文摘In the realm of the synthesis of heat-integrated distillation configurations,the conventional approach for exploring more heat integration possibilities typically entails the splitting of a single column into a twocolumn configuration.However,this approach frequently necessitates tedious enumeration procedures,resulting in a considerable computational burden.To surmount this formidable challenge,the present study introduces an innovative remedy:The proposition of a superstructure that encompasses both single-column and multiple two-column configurations.Additionally,a simultaneous optimization algorithm is applied to optimize both the process parameters and heat integration structures of the twocolumn configurations.The effectiveness of this approach is demonstrated through a case study focusing on industrial organosilicon separation.The results underscore that the superstructure methodology not only substantially mitigates computational time compared to exhaustive enumeration but also furnishes solutions that exhibit comparable performance.
基金supported by the Teli Fellowship from Beijing Institute of Technology,the National Natural Science Foundation of China(Nos.52303366,22173109).
文摘In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.
基金the National Natural Science Foundation of China(21962008)Yunnan Province Excellent Youth Fund Project(202001AW070005)+1 种基金Candidate Talents Training Fund of Yunnan Province(2017PY269SQ,2018HB007)Yunnan Ten Thousand Talents Plan Young&Elite Talents Project(YNWR-QNBJ-2018-346).
文摘Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.
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.
基金The authors are grateful for the financial support from National Natural Science Foundation of China(32001728).
文摘Free amino acid(FAA)is the important component of vinegar that infl uences quality perception and consumer acceptance.FAA is one of the major metabolites produced by microorganisms;however,the microbial metabolic network on FAA biosynthesis remains unclear.Through metagenomic analysis,this work aimed to elucidate the roles of microbes in FAA biosynthesis during Monascus rice vinegar fermentation.Taxonomic profiles from functional analyses showed 14 dominant genera with high contributions to the metabolism pathways.The metabolic network for FAA biosynthesis was then constructed,and the microbial distribution in different metabolic pathways was illuminated.The results revealed that 5 functional genera were closely involved in FAA biosynthesis.This study illuminated the metabolic roles of microorganisms in FAA biosynthesis and provided crucial insights into the functional attributes of microbiota in vinegar fermentation.
基金the financial support from by the National Key Research and Development Program of China(No.2022YFB4101800)National Natural Science Foundation of China(No.22278298)Program for Introducing Talents of Discipline to Universities of China(No.BP0618007).
文摘Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.
基金the funding from Natural Science Foundation of China(No.52003163)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515010670)+1 种基金Science and Technology Innovation Commission of Shenzhen(Nos.KQTD20170810105439418 and 20200812112006001)NTUT-SZU Joint Research Program(Nos.2022005 and 2022015)
文摘Developing a simple scalable method to fabricate electrodes with high capacity and wide voltage range is desired for the real use of electrochemical supercapacitors.Herein,we synthesized amorphous NiCo-LDH nanosheets vertically aligned on activated carbon cloth substrate,which was in situ transformed from Co-metal-organic framework materials nano-columns by a simple ion exchange process at room temperature.Due to the amorphous and vertically aligned ultrathin structure of NiCo-LDH,the NiCo-LDH/activated carbon cloth composites present high areal capacities of 3770 and 1480 mF cm^(-2)as cathode and anode at 2 mA cm^(-2),and 79.5%and 80%capacity have been preserved at 50 mA cm^(-2).In the meantime,they all showed excellent cycling performance with negligible change after>10000 cycles.By fabricating them into an asymmetric supercapacitor,the device achieves high energy densities(5.61 mWh cm^(-2)and 0.352 mW cm^(-3)).This work provides an innovative strategy for simplifying the design of supercapacitors as well as providing a new understanding of improving the rate capabilities/cycling stability of NiCo-LDH materials.
基金supported by China National Natural Science Foundation(22008260,21908123)。
文摘Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.
基金the Science and Engineering Research Board(SERB),Government of India for funding this work(Sanction No.EEQ/2021/001116)。
文摘The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia synthesis.While the process is thermodynamically feasible at ambient temperature and pressure,challenges such as the competing hydrogen evolution reaction,low nitrogen solubility in electrolytes,and the activation of inert dinitrogen(N_(2))gas adversely affect the performance of ammonia production.These hurdles result in low Faradaic efficiency and low ammonia production rate,which pose obstacles to the commercialisation of the process.Researchers have been actively designing and proposing various electrocatalysts to address these issues,but challenges still need to be resolved.A key strategy in electrocatalyst design lies in understanding the underlying mechanisms that govern the success or failure of the electrocatalyst in driving the electrochemical reaction.Through mechanistic studies,we gain valuable insights into the factors affecting the reaction,enabling us to propose optimised designs to overcome the barriers.This review aims to provide a comprehensive understanding of the various mechanisms involved in eNRR on the electrocatalyst surface.It delves into the various mechanisms such as dissociative,associative,Mars-van Krevelen,lithium-mediated nitrogen reduction and surface hydrogenation mechanisms of nitrogen reduction.By unravelling the intricacies of eNRR mechanisms and exploring promising avenues,we can pave the way for more efficient and commercially viable ammonia synthesis through this sustainable electrochemical process by designing an efficient electrocatalyst.
基金National Natural Science Foundation of China(Grant No.22005275)to provide fund for conducting experiments.
文摘In order to improve the energy output consistency of 3, 3’-diamino-4, 4’-azoxyfurazan(DAAF) in the new insensitive booster and the safety and efficiency in the preparation process, a continuous preparation system of DAAF from synthesis to spherical coating was designed and established in this paper, which combined ultrasonic micromixing reaction with microdroplet globular template. In the rapid micromixing stage, the microfluidic mixing technology with ultrasonic was used to synergistically strengthen the uniform and rapid mass transfer mixing reaction between raw materials to ensure the uniformity of DAAF particle nucleation-growth, and to prepare high-quality DAAF crystals with uniform structure and morphology and concentrated particle size distribution. In the microdroplet globular template stage, the microfluidic droplet technology was used to form a droplet globular template with uniform size under the shear action of the continuous phase of the dispersed phase solution containing DAAF particles and binder. The size of the droplet template was controlled by adjusting the flow rate ratio between the continuous phase and the dispersed phase. In the droplet globular template, with the diffusion of the solvent in the dispersed phase droplets, the binder precipitates to coat the DAAF into a ball, forming a DAAF microsphere with high sphericity, narrow particle size distribution and good monodispersity. The problem of discontinuity and DAAF particle suspension in the process was solved, and the coating theory under this process was studied. DAAF was coated with different binder formulations of fluororubber(F2604), nitrocellulose(NC) and NC/glycidyl azide polymer(GAP), and the process verification and evaluation of the system were carried out. The balling effects of large, medium and small droplet templates under different binder formulations were studied. The scanning electron microscope(SEM) results show that the three droplet templates under the three binder formulations exhibit good balling effect and narrow particle size distribution. The DAAF microspheres were characterized by powder X-ray diffraction(XRD), differential scanning calorimetry(DSC), thermo-gravimetric(TG) and sensitivity analyzer. The results showed that the crystal structure of DAAF did not change during the process, and the prepared DAAF microspheres had lower decomposition temperature and lower mechanical sensitivity than raw DAAF. The results of detonation parameters show that the coating of DAAF by using the above three binder formulations will not greatly reduce the energy output of DAAF, and has comparable detonation performance to raw DAAF. This study proves an efficient and safe continuous system from synthesis to spherical coating modification of explosives, which provides a new way for the continuous, safe and efficient preparation of spherical explosives.
文摘The coal-to-ethanol process,as the clean coal utilization,faces challenges from the energy-intensive distillation that separates multi-component effluents for pure ethanol.Referring to at least eight columns,the synthesis of the ethanol distillation system is impracticable for exhaustive comparison and difficult for conventional superstructure-based optimization as rigorous models are used.This work adopts a superstructure-based framework,which combines the strategy that adaptively selects branches of the state-equipment network and the parallel stochastic algorithm for process synthesis.High-performance computing significantly reduces time consumption,and the adaptive strategy substantially lowers the complexity of the superstructure model.Moreover,parallel computing,elite search,population redistribution,and retention strategies for irrelevant parameters are used to improve the optimization efficiency further.The optimization terminates after 3000 generations,providing a flowsheet solution that applies two non-sharp splitting options in its distillation sequence.As a result,the 59-dimension superstructure-based optimization was solved efficiently via a differential evolution algorithm,and a high-quality solution with a 28.34%lower total annual cost than the benchmark was obtained.Meanwhile,the solution of the superstructure-based optimization is comparable to that obtained by optimizing a single specific configuration one by one.It indicates that the superstructure-based optimization that combines the adaptive strategy can be a promising approach to handling the process synthesis of large-scale and complex chemical processes.
基金supported by the Starting Foundation of ShanghaiTech Universitythe Double First-Class Initiative Fund of ShanghaiTech Universitythe National Natural Science Foundation of China (21972092)
文摘Oxynitride semiconductors are promising photocatalyst materials for visible light-driven water splitting,while the synthesis of well crystalized oxynitride still remains challenge.In present work,narrow-bandgap TaON nanoparticles are synthesized via heating a vacuum-sealed mixture of KTaO_(3),Ta and NH_(4)Cl.This method possesses multiple advantages in terms of lower calcination parameter,higher N conversion efficiency and superior photocatalytic activity in comparison with the traditional thermal ammonolysis using NH_(3) gas as a nitrogen source.Through the analysis of intermediates produced upon the elevation of heating temperature,a gas-solid-phase reaction between TaCl_(5) and Ta_(2)O_(5) is demonstrated as the final step,which is conducive to decreasing thermal energy barrier and accelerating nitridation process.Precise control of preparation conditions,including calcination temperature and duration,allows for the regulation of surface O/N ratio of TaON particles to unity,resulting in optimized photocat-alytic activity.Photoelectrochemical assessment and intensity modulated photocurrent spectroscopy provide convincing evidence for improved charge transfer effciency of photoexcited holes at TaON surface.A Z-scheme overall water splitting is accomplished by employing the TaON as an effective oxygen evolution photocatalyst,SrTiO_(3):Rh as a hydrogen evolution photocatalyst,and reduced graphene oxide(rGO)as a solid-state electron mediator.This work presents a promising strategy for the synthesis of high-quality oxynitride materials in application to photocatalytic water splitting.
基金Supported by Key Scientific Research Platforms and Projects of Guangdong Regular Institutions of Higher Education of China(Grant No.2022KCXTD033)Guangdong Provincial Natural Science Foundation of China(Grant No.2023A1515012103)+1 种基金Guangdong Provincial Scientific Research Capacity Improvement Project of Key Developing Disciplines of China(Grant No.2021ZDJS084)National Natural Science Foundation of China(Grant No.52105009).
文摘The current parallel ankle rehabilitation robot(ARR)suffers from the problem of difficult real-time alignment of the human-robot joint center of rotation,which may lead to secondary injuries to the patient.This study investigates type synthesis of a parallel self-alignment ankle rehabilitation robot(PSAARR)based on the kinematic characteristics of ankle joint rotation center drift from the perspective of introducing"suitable passive degrees of freedom(DOF)"with a suitable number and form.First,the self-alignment principle of parallel ARR was proposed by deriving conditions for transforming a human-robot closed chain(HRCC)formed by an ARR and human body into a kinematic suitable constrained system and introducing conditions of"decoupled"and"less limb".Second,the relationship between the self-alignment principle and actuation wrenches(twists)of PSAARR was analyzed with the velocity Jacobian matrix as a"bridge".Subsequently,the type synthesis conditions of PSAARR were proposed.Third,a PSAARR synthesis method was proposed based on the screw theory and type of PSAARR synthesis conducted.Finally,an HRCC kinematic model was established to verify the self-alignment capability of the PSAARR.In this study,93 types of PSAARR limb structures were synthesized and the self-alignment capability of a human-robot joint axis was verified through kinematic analysis,which provides a theoretical basis for the design of such an ARR.
基金supported by the Fundamental Research Grant Scheme by Ministry of Higher Education Malaysia(FRGS/1/2021/STG04/XMU/02/1 and FRGS/1/2022/TK09/XMU/03/2)the Xiamen University Malaysia Research Fund(XMUMRF/2023-C11/IENG/0056)。
文摘MXene has been the limelight for studies on electrode active materials,aiming at developing supercapacitors with boosted energy density to meet the emerging influx of wearable and portable electronic devices.Despite its various desirable properties including intrinsic flexibility,high specific surface area,excellent metallic conductivity and unique abundance of surface functionalities,its full potential for electrochemical performance is hindered by the notorious restacking phenomenon of MXene nanosheets.Ascribed to its two-dimensional(2D)nature and surface functional groups,inevitable Van der Waals interactions drive the agglomeration of nanosheets,ultimately reducing the exposure of electrochemically active sites to the electrolyte,as well as severely lengthening electrolyte ion transport pathways.As a result,energy and power density deteriorate,limiting the application versatility of MXene-based supercapacitors.Constructing 3D architectures using 2D nanosheets presents as a straightforward yet ingenious approach to mitigate the fatal flaws of MXene.However,the sheer number of distinct methodologies reported,thus far,calls for a systematic review that unravels the rationale behind such 3D MXene structural designs.Herein,this review aims to serve this purpose while also scrutinizing the structure–property relationship to correlate such structural modifications to their ensuing electrochemical performance enhancements.Besides,the physicochemical properties of MXene play fundamental roles in determining the effective charge storage capabilities of 3D MXene-based electrodes.This largely depends on different MXene synthesis techniques and synthesis condition variations,hence,elucidated in this review as well.Lastly,the challenges and perspectives for achieving viable commercialization of MXene-based supercapacitor electrodes are highlighted.
基金supported by the National Natural Science Foundation of China(52174277,52204309 and 52374300).
文摘High alumina fly ash(FAHAl)is a kind of bulk solid waste unique to China,whose availability of high-value aluminum and the threat to the environment makes its high-value utilization urgent.In this work,the alumina containing leaching solution obtained from Na_(2)CO_(3) roasting and HCl leaching of FAHAl was used as the mother liquor to prepare layered boehmite in situ.The preparation process with AlCl_(3) as the raw material was also compared.The formation process and mechanism of boehmite,the choice of solvent,along with the adsorption capability of Congo red were analyzed by X-ray diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,Brunauer-Emmett-Teller method and adsorption experiments.Results showed that during the preparation of layered boehmite,the precursor Al(OH)_(3) from the reaction of Al^(3+) and OH-is transformed into boehmiteγ-AlOOH.The existence of ethanol is beneficial to regulate and promote the growth of boehmite crystal effectively.When water and ethanol are mixed with a volume ratio of 2:1 and used as the solvent,the maximum specific surface area of the boehmite is obtained at 135.7 m^(2)·g^(-1),and 99.16%of Congo red can be absorbed after 10 min when AlCl3 is used as a raw material.As purified leaching solution is used as the mother liquid,the crystallinity of boehmite decreases slightly when the pH value decreases from 12.5 to 11.When pH is 11,the removal efficiency of Congo red reaches a maximum of 72.25%.This process not only achieves the extraction of aluminum and high-value utilization of FAHAl but also provides a thought to prepare layered boehmite with adsorption properties.
