Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

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.

The structure-directing role of heterologous seeds in the synthesis of zeolite

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.

Facile synthesis of hierarchical NaX zeolite from natural kaolinite for efficient Knoevenagel condensation

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.

Optimal synthesis of heat-integrated distillation configurations using the two-column superstructure

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.

Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

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.

Recent advances in cobalt phosphide-based materials for electrocatalytic water splitting:From catalytic mechanism and synthesis method to optimization design

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.

Microfluidic-oriented synthesis of enriched iridium nanodots/carbon architecture for robust electrocatalytic nitrogen fixation

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.

Metagenomic analysis revealing the metabolic role of microbial communities in the free amino acid biosynthesis of Monascus rice vinegar during fermentation

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.

Boosting Fischer-Tropsch Synthesis via Tuning of N Dopants in TiO_(2)@CN-Supported Ru Catalysts

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%.

Room Temperature Synthesis of Vertically Aligned Amorphous Ultrathin NiCo-LDH Nanosheets Bifunctional Flexible Supercapacitor Electrodes

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.

Synthesis of mordenite by solvent-free method and its application in the dimethyl ether carbonylation reaction

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.

Efficient electrocatalytic urea synthesis from CO_(2)and nitrate over the scale-up produced FeNi alloy-decorated nanoporous carbon

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.

Exploring nitrogen reduction reaction mechanisms in electrocatalytic ammonia synthesis:A comprehensive review

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.

Process and performance of DAAF microspheres prepared by continuous integration from synthesis to spherical coating based on microfluidic system

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.

Process synthesis for the separation of coal-to-ethanol products

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.

Type Synthesis of Self-Alignment Parallel Ankle Rehabilitation Robot with Suitable Passive Degrees of Freedom

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.

Solvothermal synthesis and adsorption performance of layered boehmite using aluminum chloride and high-alumina fly ash

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.

NH_(4)Cl-assisted synthesis of TaON nanoparticle applied to photocatalytic hydrogen and oxygen evolution from water

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.

Sustainable ammonia synthesis:An in-depth review of non-thermal plasma technologies

Ammonia serves both as a widely used fertilizer and environmentally friendly energy source due to its high energy density,rich hydrogen content,and emissions-free combustion.Additionally,it offers convenient transportation and storage as a hydrogen carrier.The dominant method used for large-scale ammonia production is the Haber-Bosch process,which requires high temperatures and pressures and is energy-intensive.However,non-thermal plasma offers an eco-friendly alternative for ammonia synthesis,gaining significant attention.It enables ammonia production at lower temperatures and pressures using plasma technology.This review provides insights into the catalyst and reactor developments,which are pivotal for promoting ammonia efficiency and addressing existing challenges.At first,the reaction kinetics and mechanisms are introduced to gain a comprehensive understanding of the reaction pathways involved in plasma-assisted ammonia synthesis.Thereafter,the enhancement of ammonia synthesis efficiency is discussed by developing and optimizing plasma reactors and effective catalysts.The effect of other feeding sources,such as water and methane,instead of hydrogen is also presented.Finally,the challenges and possible solutions are outlined to facilitate energy-saving and enhance ammonia efficiency in the future.