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.

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.

Statistical analysis on the validity of the cold plasma approximation for chorus waves based on Van Allen Probe observations and their effects on radiation belt electrons

Theoretical analysis has demonstrated that the dispersion relation of chorus waves plays an essential role in the resonant interaction and energy transformation between the waves and magnetospheric electrons.Previous quantitative analyses often simplified the chorus dispersion relation by using the cold plasma assumption.However,the applicability of the cold plasma assumption is doubtful,especially during geomagnetic disturbances.We here present a systematic statistical analysis on the validity of the cold plasma dispersion relation of chorus waves based on observations from the Van Allen Probes over the period from 2012 to 2018.The statistical results show that the observed magnetic field intensities deviate substantially from those calculated from the cold plasma dispersion relation and that they become more pronounced with an increase in geomagnetic activity or a decrease in background plasma density.The region with large deviations is mainly concentrated in the nightside and expands in both the radial and azimuthal directions as the geomagnetic activity increases or the background plasma density decreases.In addition,the bounce-averaged electron scattering rates are computed by using the observed and cold plasma dispersion relation of chorus waves.Compared with usage of the cold plasma dispersion relation,usage of the observed dispersion relation considerably lowers the minimum resonant energy of electrons and lowers the scattering rates of electrons above tens of kiloelectronvolts but enhances those below.Furthermore,these differences are more pronounced with the enhancement of geomagnetic activity or the decrease in background plasma density.

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.

Mechanical and Morphological Properties of Highly Dispersed Carbon Nanotubes Reinforced Cement Based Materials

Stable homogeneous suspensions of multi-walled carbon nanotubes （MWCNTs） were prepared using gum arabic （GA） as dispersant and were incorporated to Portland cement paste. The dispersion was examined by ultraviolet visible spectroscopy （UV-vis）, and the concentration measurement shows that the optimum concentration of GA is 0.45 g · L^-1. The dispersibility of the surface-modified MWCNTs in aqueous solution and cement matrix were investigated by transmission electron microscopy （TEM） and energy dispersive spectroscopy （EDS）, and the mechanical properties of the composites were investigated. The results show that the addition of the treated nanotubes can improve both the flexural strength and the compressive strength of the Portland cement composite significantly. The flexural strength of the composite increases up to 43.38% with the MWCNT concentration of 0.08% （by weight of cement）. The porosity and pore size distribution of the composites were measured by mercury intrusion porosimetry （MIP）, and the results indicate that the cement paste doped with MWCNTs obtained lower porosity and concentrated pore size distribution. The morphological structure was analyzed by field emission scanning electron microscopy （FESEM） and EDS. It is shown that MWCNTs act as bridges and networks across cracks and voids, which transfer the load in case of tension, and the interface bond strength between the nanotubes and matrix is very strong.

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.

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.

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.

Corrosion resistance evaluation of highly dispersed MgO–MgAl2O4–ZrO2 composite and analysis of its corrosion mechanism: A chromium-free refractory for RH refining kilns

The corrosion resistance behavior of a highly dispersed MgO-MgAl2O4-ZrO2 composite refractory material is examined by testing with high-basicity and low-basicity RH(Ruhrstahl-Hereaeus)slags.The composite material exhibits greater resistance to the RH slags than the traditional MgO-Cr2O3 composite,MgO-ZrO2 composite,and MgO-MgAl2O4-ZrO2 composite.On the basis of the microstructural analysis and mechanisms calculations,the corrosion resistance behavior of the MgO-MgAl2O4-ZrO2 composite is attributable to its highly dispersed structure,which helps protect the high activity of ZrO2.When in contact with the slag,ZrO2 reacts with CaO to form the stable phase CaZrO3,which protects MgAl2O4 against corrosion,thereby enhancing the corrosion resistance of the composite.

Interaction Between Large-scale Vortex Structure and Dispersed Particles in a Three Dimensional Mixing Layer

In order to understand the interaction between large-scale vortex structure and particles, a two-way coupling temporal mixing layer laden with particles at a Stokes number of 5 with different mass loading planted initially in the upper half region is numerically studied. The pseudospectral method is used for the flow fluid and the Lagrangian approach is employed to trace particles. The momentum coupling effect introduced by a particle is approximated to a point force. The simulation results show that the coherent structures are still dominant in the mixing layer, but the large-scale vortex structure and particle dispersion are modulated. The length of large-scale vortex structure is shortened and the pairing is delayed. At the same time, the particles are distributed more evenly in the whole flow field as the mass loading is increased, but the particle dispersion along the transverse direction differs from that along the spanwise direction, which indicates that the effect by the addition of particle on the spanwise large-scale vortex structure is different from the streamwise counterpart.

Atomically Dispersed Dual‑Metal Sites Showing Unique Reactivity and Dynamism for Electrocatalysis

The real structure and in situ evolution of catalysts under working conditions are of paramount importance,especially for bifunctional electrocatalysis.Here,we report asymmetric structural evolution and dynamic hydrogen-bonding promotion mechanism of an atomically dispersed electrocatalyst.Pyrolysis of Co/Ni-doped MAF-4/ZIF-8 yielded nitrogen-doped porous carbons functionalized by atomically dispersed Co–Ni dual-metal sites with an unprecedented N8V4 structure,which can serve as an efficient bifunctional electrocatalyst for overall water splitting.More importantly,the electrocatalyst showed remarkable activation behavior due to the in situ oxidation of the carbon substrate to form C–OH groups.Density functional theory calculations suggested that the flexible C–OH groups can form reversible hydrogen bonds with the oxygen evolution reaction intermediates,giving a bridge between elementary reactions to break the conventional scaling relationship.

Prediction of dispersed phase holdup in pulsed disc and doughnut solvent extraction columns under different mass transfer conditions

Using experimental data from a number of pulsed disc and doughnut solvent extraction columns, a unified correla- tion for the prediction of dispersed phase holdup that considers the effects of mass transfer is presented. Pulsed disc and doughnut solvent extraction columns （PDDC） have been used for a range of important applications such as ura- nium extraction and nuclear fuel recycling. Although the dispersed phase holdup in a PDDC has been presented by some researchers, there is still the need to develop a robust correlation that can predict the experimental dispersed phase holdup over a range of operating conditions including the effects of mass transfer direction. In this study, dis- persed phase holdup data from different literature sources for a PDDC were used to refit constants for the correlation presented by Kumar and Hartland lind. Eng. Chem. Res.,27 （1988）,131-138] which did not consider the effect of col- umn geometry. In order to incorporate the characteristic length of the PDDC （i.e. the plate spacing）, the unified cor- relation for holdup proposed by Kumar and Hartland based on data from eight different types of columns [Ind. Eng. Chem. Res.,34 （1995） 3925-3940] was refitted to the PDDC data. New constants have been presented for each hold- up correlation for a PDDC based on regression analysis using published holdup data from PDDCs that cover a range of onerating conditions and nhwical nronerties and consider the direction of mass transfer.

Ru/FeO_x catalyst performance design: Highly dispersed Ru species for selective carbon dioxide hydrogenation

A series of Ru/FeOx catalysts were synthesized for the selective hydrogenation of CO2to CO.Detailed characterizations of the catalysts through X‐ray diffraction,X‐ray photoelectron spectroscopy,transmission electron microscopy,and temperature‐programmed techniques were performed to directly monitor the surface chemical properties and the catalytic performance to elucidate the reaction mechanism.Highly dispersed Ru species were observed on the surface of FeOx regardless of the initial Ru loading.Varying the Ru loading resulted in changes to the Ru coverage over the FeOx surface,which had a significant impact on the interaction between Ru and adsorbed H,and concomitantly,the H2activation capacity via the ability for H2dissociation.FeOx having0.01%of Ru loading exhibited100%selectivity toward CO resulting from the very strong interaction between Ru and adsorbed H,which limits the desorption of the activated H species and hinders over‐reduction of CO to CH4.Further increasing the Ru loading of the catalysts to above0.01%resulted in the adsorbed H to be easily dissociated,as a result of a weaker interaction with Ru,which allowed excessive CO reduction to produce CH4.Understanding how to selectively design the catalyst by tuning the initial loading of the active phase has broader implications on the design of supported metal catalysts toward preparing liquid fuels from CO2.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences toward preparing liquid fuels from CO2.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.