Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.

Atomically Dispersed Ruthenium Catalysts with Open Hollow Structure for Lithium-Oxygen Batteries

Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.

Atomic Dispersed Hetero‑Pairs for Enhanced Electrocatalytic CO_(2)Reduction

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.

Distributed Resource Allocation in Dispersed Computing Environment Based on UAV Track Inspection in Urban Rail Transit

With the rapid development of urban rail transit,the existing track detection has some problems such as low efficiency and insufficient detection coverage,so an intelligent and automatic track detectionmethod based onUAV is urgently needed to avoid major safety accidents.At the same time,the geographical distribution of IoT devices results in the inefficient use of the significant computing potential held by a large number of devices.As a result,the Dispersed Computing(DCOMP)architecture enables collaborative computing between devices in the Internet of Everything(IoE),promotes low-latency and efficient cross-wide applications,and meets users’growing needs for computing performance and service quality.This paper focuses on examining the resource allocation challenge within a dispersed computing environment that utilizes UAV inspection tracks.Furthermore,the system takes into account both resource constraints and computational constraints and transforms the optimization problem into an energy minimization problem with computational constraints.The Markov Decision Process(MDP)model is employed to capture the connection between the dispersed computing resource allocation strategy and the system environment.Subsequently,a method based on Double Deep Q-Network(DDQN)is introduced to derive the optimal policy.Simultaneously,an experience replay mechanism is implemented to tackle the issue of increasing dimensionality.The experimental simulations validate the efficacy of the method across various scenarios.

Far-Field Behavior of Supercritical CO_(2)Being Dispersed Due to Leakage from Pipelines

Transporting massive quantities of carbon dioxide through a pipeline in its supercritical state is extremely convenient.Because of the unique properties of supercritical carbon dioxide,however,leakage occurring in such conditions can be extremely intricate,resulting in the dispersion area following leakage being influenced by numerous factors.In this study,this problem is addressed in the frame of the so-called Unified Dispersion Model(UDM),and various influential parameters are considered,namely,leakage pressure,leakage temperature,leakage aperture,leakage angle,atmospheric stability,wind speed,and surface roughness.The results show that the supercritical carbon dioxide dispersion is primarily influenced by high air temperatures,low wind speeds,reduced surface roughness,and release temperatures slightly below the critical temperature.Additionally,leak apertures also contribute to the dispersion.The dispersion is maximized under atmospheric stable D conditions,and when the leakage angle is 0°,the farthest downwind distance is 10 times greater than that at a leakage angle of 90°under the same conditions.

Measurement and Correlation of Solubilities of C.I. Disperse Red 73,C.I. Disperse Blue 183 and Their Mixture in Supercritical Carbon Dioxide

The solubility of disperse dyes and their mixture in supercritical carbon dioxide is an important property in study and development of supercritical fluid dyeing technology.In this study,solubilities of C.I.Disperse Red 73,C.I.Disperse Blue 183 and their mixture in supercritical CO2 are measured at temperatures from 343.2 to 383.2 K and pressures from 12 to 28 MPa with a static recirculation method.Under the experimental conditions for the binary(C.I.Disperse Red 73+CO2 or C.I.Disperse Blue 183+CO2) and ternary(C.I.Disperse Red 73+C.I.Disperse Blue 183+CO2) systems,the solubilities increase with pressure.The solubility of C.I.Disperse Blue 183 decreases with the increase of temperature when the pressure is lower than 16 MPa,and the trend is opposite when the pressure is higher than 16 MPa.However,there is no crossover pressure for C.I.Disperse Red 73.The solubilities are also affected by molecular polarity of dyes.The co-solvent effect exhibited in the dissolving process of mixed dyes promotes their dissolution in supercritical CO2.The experimental data of solubilities of C.I.Disperse Red 73,C.I.Disperse Blue 183,and their mixture are correlated with the Chrastil model and Mendez-Santiago/Teja model. The former is more accurate.

Experimental Determination of the Vibrational Constants of FeS（X5 △） by Dispersed Fluorescence Spectroscopy

Based on previous laser-induced fluorescence excitation spectroscopy work, the vibrational constants of neutral FeS in the X5 △ electronic state were obtained by directly mapping the ground-state vibrational levels up to v＂=3 using conventional laser-induced dispersed fluorescence spectroscopy. The vibrational frequency of FeS（X5 △） （518±5 cm-1） agrees well with that reported in a recent PES measurement （520±30 cm-1） [J. Phys. Chem. A 107, 2821 （2003）] which is the only one prior experimental vibrational frequency value for the 5 △ state of FeS. Careful comparisons of our experimental results and those documented in the literature （mainly from theoretical predictions） suggest that the ground state of FeS is 5 △ state.

Dyeing PET Textile with C.I.Disperse Red 60 and C.I. Disperse Orange 25 in Supercritical CO_2

For a better understanding of the feasibility of supercritieal fluid dyeing （SFD） and more available information for the process development, the experiments of dyeing PET textile with C.I. disperse red 60 （anthraquinone type） and C. I. disperse orange 25 （azo type） in supercritieal CO2 were carried out with a high-pressure dyeing apparatus at temperatures from 80 to 130℃ and pressure up to 31 MPa. The effect of operating conditions on color yield （K/S） was investigated in SFD experiment, and the optimum operating conditions for the above two disperse dyes were obtained as follows： the temperature 120℃, the pressure 25 MPa and the dyeing time 100 min. As compared with SFD, the conventional water dyeing （CWD） was carried out with the same dyes and textile. The results show that the better fastness, levelness and apparent color can be achieved in SFD and the SFD process has many significant advantages over the CWD process.

电解法处理C.I. Reactive Red 241、C.I. Disperse Blue 56模拟染料废水的研究

以C.I.Reactive Red 241、C.I.Disperse Blue 56模拟染料废水为对象,研究了电解法处理该类染料废水的优化条件。考察了起始电压、电解时间、溶液初始p H对处理效果的影响。结果表明,在p H=7,U=14V、I=3.2A、t=30min的条件下,C.I.Reactive Red241模拟染料废水的脱色率可达到86%以上;在p H=7,U=14V、I=3.2A、t=25min的条件下,C.I.Disperse Blue 56模拟染料废水的脱色率可达到79以上%。

A Fe-N-C catalyst with highly dispersed iron in carbon for oxygen reduction reaction and its application in direct methanol fuel cells

Exploring non‐precious metal catalysts for the oxygen reduction reaction （ORR） is essential for fuel cells and metal–air batteries. Herein, we report a Fe‐N‐C catalyst possessing a high specific surface area （1501 m2/g） and uniformly dispersed iron within a carbon matrix prepared via a two‐step pyrolysis process. The Fe‐N‐C catalyst exhibits excellent ORR activity in 0.1 mol/L NaOH electrolyte （onset potential, Eo=1.08 V and half wave potential, E1/2=0.88 V vs. reversible hydrogen electrode） and 0.1 mol/L HClO4 electrolyte （Eo=0.85 V and E1/2=0.75 V vs. reversible hydrogen electrode）. The direct methanol fuel cells employing Fe‐N‐C as the cathodic catalyst displayed promising per‐formance with a maximum power density of 33 mW/cm2 in alkaline media and 47 mW/cm2 in acidic media. The detailed investigation on the composition–structure–performance relationship by X‐ray diffraction, X‐ray photoelectron spectroscopy and Mo-ssbauer spectroscopy suggests that Fe‐N4, together with graphitic‐N and pyridinic‐N are the active ORR components. The promising direct methanol fuel cell performance displayed by the Fe‐N‐C catalyst is related to the intrinsic high catalytic activity, and critically for this application, to the high methanol tolerance.

Laser-induced Fluorescence and Dispersed Fluorescence Spectroscopy of NiB： Identification of a New 2П State in 19000-22100 cm^-1

The laser-induced fluorescence excitation spectra of jet-cooled NiB radicals have been recorded in the energy range of 19000-22100 cm-1. Eleven bands have been assigned to the [20.77]2П-X2∑＋ transition system for the first time. The dispersed fluorescence spectra related to most of these bands have been investigated. Vibrationally excited levels of the ground electronic state, with v＂ up to 6, have been observed. In addition, the lifetimes for almost all the observed bands have also been measured.

电催化-光化联合技术处理Disperse Red 3B染料废水

以Disperse Red 3B染料废水为对象,研究了电催化-光化物化组合技术处理该类染料废水的优化条件。考察了电解温度、电解质NaCl浓度、流速、染液初始pH值对处理效果的影响,且后续加入紫外光汞灯探究物化组合技术对处理效果的影响。结果表明,在T=30℃、C_(NaCl)=0.20g/L、V=65.46μl/min、pH=3的条件下,Disperse Red 3B染料废水的脱色率可达到88%以上,继续光照30mins后,COD去除率可以提升3%左右。

Controlled-release Properties of Microencapsulated Disperse Dyes

Some disperse dyes were microencapsulated by means of in- situ polymerization. These microencapsulated disperse dyes was extracted respectively by ethanol under certain conditions. The controlled-release properties of disperse dyes through the shell of microcapsules were measured by spectrophotometer. According to the results, it was drawn that the type of disperse dyes, the auxiliaries contained in disperse dyes, the quantity of system controlling medium used and the core/shell ratio of microcapsules play important roles in controlling the release properties of microcapsules. The different controlled- release properties of microcapsules, which were prepared under given conditions, however, would in turn influence the performance of microcapsules in multiple-transfer printing.

Adsorption of Disperse Blue SBL dye by synthesized poorly crystalline hydroxyapatite

The present study has been undertaken to evaluate the adsorption in batch mode of a disperse dye (Disperse Blue SBL) by poorly crystalline hydroxyapatite synthesized by coprecipitation between Ca(NO3)2and (NH4)2HPO4 reagents in aqueous solution at room temperature. The adsorption experiments were carried out to investigate the factors that influence the dye uptake by the adsorbent, such as the contact time under agitation, adsorbent dosage, initial dye concentration, solution temperature, and pH. The experimental results show that the percentage of dye removal increases with increasing the amount of adsorbent, until the total discoloration. The adsorption isotherms follow the model of Langmuir with a high adsorption capacity. The adsorption was pH and temperature dependent.

Mass Transfer Enhancement of Gas Absorption by Adding the Dispersed Organic Phases

Mass transfer enhancement of gas absorption by adding a dispersed organic phase has been studied in this work. Various dispersed organic phases （heptanol, octanol, isoamyl alcohol, heptane, octane, and isooctane） were tested respectively in the experiment. According to the theoretical model and experimental data, the overall volumetric mass transfer coefficient and enhancement factor were obtained under different dispersed organic phase volume fraction and stirring speed. The experimental results indicate that gas-liquid mass transfer is enhanced at different level by adding a dispersed organic phase. The best performance of enhancement were achieved with the dispersed organic phase volumetric fraction of 5% and under an intermediate stirring speed of 670 r·min^-1. Among the organic phases tested in the experiment, alcohols show better performance, which gave 20% higher enhance-ment of overall volumetric mass transfer coefficient than adding alkanes.

Tuning Atomically Dispersed Fe Sites in Metal–Organic Frameworks Boosts Peroxidase‑Like Activity for Sensitive Biosensing

Although nanozymes have been widely developed,accurate design of highly active sites at the atomic level to mimic the electronic and geometrical structure of enzymes and the exploration of underlying mechanisms still face significant challenges.Herein,two functional groups with opposite electron modulation abilities(nitro and amino)were introduced into the metal–organic frameworks(MIL-101(Fe))to tune the atomically dispersed metal sites and thus regulate the enzymelike activity.Notably,the functionalization of nitro can enhance the peroxidase(POD)-like activity of MIL-101(Fe),while the amino is poles apart.Theoretical calculations demonstrate that the introduction of nitro can not only regulate the geometry of adsorbed intermediates but also improve the electronic structure of metal active sites.Benefiting from both geometric and electronic effects,the nitro-functionalized MIL-101(Fe)with a low reaction energy barrier for the HO*formation exhibits a superior POD-like activity.As a concept of the application,a nitro-functionalized MIL-101(Fe)-based biosensor was elaborately applied for the sensitive detection of acetylcholinesterase activity in the range of 0.2–50 mU mL−1 with a limit of detection of 0.14 mU mL−1.Moreover,the detection of organophosphorus pesticides was also achieved.This work not only opens up new prospects for the rational design of highly active nanozymes at the atomic scale but also enhances the performance of nanozyme-based biosensors.

Advances in Studies on Turbulent Dispersed Multiphase Flows

Dispersed multiphase flows,including gas-particle(gas-solid),gas-spray,liquid-particle(liquid-solid) ,liquid-bubble,and bubble-liquid-particle flows,are widely encountered in power,chemical and metallurgical,aeronautical and astronautical,transportation,hydraulic and nuclear engineering. In this paper,advances and re-search needs in fundamental studies of dispersed multiphase flows,including the particle/droplet/bubble dynamics,particle-particle,droplet-droplet and bubble-bubble interactions,gas-particle and bubble-liquid turbulence interac-tions,particle-wall interaction,numerical simulation of dispersed multiphase flows,including Reynolds-averaged modeling(RANS modeling),large-eddy simulation(LES) and direct numerical simulation(DNS) are reviewed. The research results obtained by the present author are also included in this review.

Hydrogenation Conversion of Phenanthrene over Dispersed Mo-based Catalysts

With oil-soluble molybdenum compound and sublimed sulfur serving as raw materials, two dispersed Mo-based catalysts were prepared, characterized and then applied to the hydrogenation conversion of phenanthrene. The test results showed that under the conditions specified by this study, the catalyst prepared in a higher sulfiding atmosphere was more catalytically active due to its higher content of MoS2 and stronger intrinsic catalytic activity of MoS2 unit, which demonstrated that the sulfiding atmosphere for the preparation of catalysts not only could influence the yield of MoS2 but also the structure of MoS2.The analysis on the selectivity of octahydrophenanthrene isomers revealed that the catalyst prepared in a lower sulfiding atmosphere had a relatively higher catalytic selectivity to the hydrogenation of outer aromatic ring and the structure of catalysts could be modified under the specific reaction conditions. Moreover, the selectivity between the isomers of as-octahydrophenanthrene at different reaction time and temperature was analyzed and, based on the results, a hydrogenation mechanism over dispersed Mo-based catalysts was suggested, with monatomic hydrogen transfer and catalytic surface desorption of the half-addition intermediates functioning as the key points. In addition, it is concluded that the catalyst prepared in a lower sulfiding atmosphere was more capable of adsorption than the other one.

Atomically Dispersed Transition Metal-Nitrogen-Carbon Bifunctional Oxygen Electrocatalysts for Zinc-Air Batteries:Recent Advances and Future Perspectives

Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs.Atomically dispersed metal-nitrogen-carbon(M-N-C)catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis.In this work,general principles for designing atomically dispersed M-N-C are reviewed.Then,strategies aiming at enhancing the bifunctional catalytic activity and stability are presented.Finally,the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined.It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.

A facile sulfur-assisted method to synthesize porous alveolate Fe/g-C3N4 catalysts with ultra-small cluster and atomically dispersed Fe sites

Heterogeneous catalysts with ultra-small clusters and atomically dispersed(USCAD)active sites have gained increasing attention in recent years.However,developing USCAD catalysts with high-density metal sites anchored in porous nanomaterials is still challenging.Here,through the template-free S-assisted pyrolysis of low-cost Fe-salts with melamine(MA),porous alveolate Fe/g-C3N4 catalysts with high-density(Fe loading up to 17.7 wt%)and increased USCAD Fe sites were synthesized.The presence of a certain amount of S species in the Fe-salts/MA system plays an important role in the formation of USCAD S-Fe-salt/CN catalysts;the S species act as a"sacrificial carrier"to increase the dispersion of Fe species through Fe-S coordination and generate porous alveolate structure by escaping in the form of SO2 during pyrolysis.The S-Fe-salt/CN catalysts exhibit greatly promoted activity and reusability for degrading various organic pollutants in advanced oxidation processes compared to the corresponding Fe-salt/CN catalysts,due to the promoted accessibility of USCAD Fe sites by the porous alveolate structure.This S-assisted method exhibits good feasibility in a large variety of S species(thiourea,S powder,and NH4SCN)and Fe salts,providing a new avenue for the low-cost and large-scale synthesis of high-density USCAD metal/g-C3N4 catalysts.