Concentration fluctuation caused by reaction-diffusion coupling near catalytic active sites

The coupling of reaction and diffusion between neighboring active sites in the catalyst pore leads to the spatiotemporal fluctuation in component concentration, which is very important to catalyst performance and hence its optimal design. Molecular dynamics simulation with hard-sphere and pseudo-particle modeling has previously revealed the non-stochastic concentration fluctuation of the reactant/product near isolated active site due to such coupling, using a simple model reaction of A → B in 2D pores. The topic is further developed in this work by studying the concentration fluctuation due to such coupling between neighboring active sites in 3D pores. Two 3D pore models containing an isolated active site and two adjacent active sites were constructed, respectively. For the isolated site, the concentration fluctuation intensifies for larger pores, but the product yield decreases, and for a given pore size, the product yield reaches a peak at a certain reactant concentration. For two neighboring sites, their distance (d) is found to have little effect on the reaction, but significant to the diffusion. For the same reaction competing at both sites, larger d leads to more efficient diffusion and better overall performance. However, for sequential reactions at the two sites, higher overall performance presents at a smaller d. The results should be helpful to the catalyst design and reaction control in the relevant processes.     

Understanding enhancing mechanism of Pr6O11 and Pr(OH)3 in methanol electrooxidation

The presence of oxygen vacancies and hydroxyl groups are both favorable for the methanol electrooxidation on Pt-based catalysts.Understanding and differentiating the enhancing mechanism between oxygen vacancies and hydroxyl groups for high activity of Pt catalysts in methanol oxidation reaction(MOR)is essential but still challenging.Herein,we developed two kinds of co-catalyst for Pt/CNTs,Pr₆O₁₁is rich in oxygen vacancies but contains substantially no hydroxyl groups,while Pr(OH)₃ possesses abundant hydroxyl groups without oxygen vacancies.After a seque nce of designed experiments,it can be found that both oxygen vacancies and hydroxyl groups can improve the performance of Pt/CNTs electrocatalysts,but the enhancing mechanism and improving degree of oxygen vacancies and hydroxyl groups for the MOR are different.Since the oxygen vacancies are more conducive to increasing the intrinsic activity of the Pt catalyst,and the hydroxyl groups play a decisive role in dehydrogenation and deproto nation of methanol,the co-catalysts with both oxygen vacancies and hydroxyl groups mixed with Pt/CNTs have higher catalytic performance.Therefore,hydroxyl-rich Pr₆O₁₁·xH₂O was prepared and used as MOR electrocatalyst after mixed with Pt/CNTs.Benefiting from the synergistic effect of oxygen vacancies and hydroxyl groups,the Pr₆O₁₁·xH₂O/Pt/CNTs shows a high peak current density of 741 mA/mg,which is three times higher than that of Pt/CNTs.These new discoveries serve as a promising strategy for the rational design of MOR catalysts with low cost and high activity.     

Reconstruction of fission events in heavy ion reactions with the compact spectrometer for heavy ion experiment

We report a reconstruction method for fast-fission events in 25 MeV/u⁸⁶Kr +²⁰⁸Pb reactions at the Compact Spectrometer for Heavy Ion Experiment（CSHINE）. The fission fragments（FFs） are measured using three large-area parallel-plate avalanche counters, which can deliver the position and arrival timing information of the fragments. The start timing information is provided by the radio frequency of the cyclotron. Fission events were reconstructed using the velocities of the two...     

Reconstruction of fission events in heavy ion reactions with the compact spectrometer for heavy ion experiment

We report a reconstruction method for fast-fission events in 25 MeV/u⁸⁶Kr +²⁰⁸Pb reactions at the Compact Spectrometer for Heavy Ion Experiment（CSHINE）. The fission fragments（FFs） are measured using three large-area parallel-plate avalanche counters, which can deliver the position and arrival timing information of the fragments. The start timing information is provided by the radio frequency of the cyclotron. Fission events were reconstructed using the velocities of the two...     

Synthesis of Hollow Three-Dimensional Channels LiNi_(0.5)Mn_(1.5)O_4 Microsphere by PEO Soft Template Assisted with Solvothermal Method

A appropriate size with three-dimension(3 D) channels for lithium diffusion plays an important role in constructing highperforming LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode materials, as it can not only reduce the transport path of lithium ions and electrons, but also reduce the side effects and withstand the structural strain in the process of repetitive Li~+ intercalation/deintercalation. In this work, an e fficient method for designing the hollow LNMO microsphere with 3 D channels structure by using polyethylene oxide(PEO) as soft template agent assisted solvothermal method is proposed. Experimental results indicate that PEO can make the reagents mingle evenly and nucleate slowly in the solvothermal process, thus obtaining a homogeneous distribution of carbonate precursors. In the final LNMO products, the hollow 3 D channels structure obtained by the decomposition of PEO and carbonate precursor in the calcination can provide abundant electroactive zones and electron/ion transport paths during the charge/discharge process, which benefits to improve the cycling performance and rate capability. The LNMO prepared by adding 1 g PEO possesses the most outstanding electrochemical performance, which presented an excellent discharge capacity of 143.1 mAh g~(-1) at 0.1 C and with a capacity retention of 92.2% after 100 cycles at 1 C. The superior performance attributed to the 3 D channels structure of hollow microspheres, which provide uninterrupted conductive systems and therefore achieve the stable transfer for electron/ion.     

Nitrogen Removal Performance of Denitrifying Ammonium Oxidation System in Treating Sulfamethoxazole-laden Secondary Wastewater Effluent

In this study,nitrogen removal performance of the denitrifying ammonium oxidation(DAO)process was investigated when treating sulfamethoxazole(SMX)-laden secondary wastewater effluent.The influent SMX concentration showed negligible effect on efficiencies for removal of nitrate and COD.However,the ammonium ions removal rate was moderately reduced,when the influent SMX concentration in wastewater reached 6 mg/L.Total nitrogen removal efficiency remained as high as 76.77%towards the day 158 at the end of experiment.Candidatus_Brocadia and Candidatus_Kuenenia were the functional anammox strains.The unclassified_f__Rhodobacteraceae sp.was predominant heterotrophic denitrifying strain in the studied reactor.The concentrations of soluble extracellular polymeric substances in sludge obviously increased from 16.76 mg/g VSS to 32.31 mg/g VSS,which might protect the nitrogen removal strains from high-concentration SMX.This result provides a theoretical and technical foundation for the application of denitrifying ammonium oxidation process in treating sulfamethoxazole-laden secondary wastewater effluent.     

Altered age-hardening behavior in the ultrafine-grained surface layer of Mg-Zn-Y-Ce-Zr alloy processed by sliding friction treatment

To gain insight into the ageing behavior of ultrafine grain(UFG)structure,the precipitation phenom-ena and microstructural evolutions of Mg-6Zn-1Y-0.4Ce-0.5 Zr(wt.％)alloy processed by sliding friction treatment(SFT)were systematically studied using hardness texting,transmission electron microscopy(TEM)equipped with high-angle annular dark-field scanning(HADDF-STEM),X-ray diffraction(XRD)and XRD line broadening analysis.The microhardness of the SFT-processed(SFTed)sample initially decreases from 109.6 HV to 104.8 HV at ageing for 8 h,and then increases to the peak-ageing point of 115.4 HV at 16 h.Subsequently,it enters the over-aged period.The un-SFTed sample,as the counterpart,follows a regular ageing behavior that increases from 89.9 HV to 99.6 HV when ageing for 12 h,and then drops.A multi-mechanistic model is established to describe the strengthening due to grain refinement,disloca-tion accumulation,precipitation etc.The analysis reveals that the temperature sensitive UFG structure has an obvious grain coarsening effect,which arouses the soft phenomenon in the early ageing stage.But precipitation hardening provides an excellent hardness enhancement for overcoming the negative influ-ence and helping to reach the peak-aged point.In our microstructural observations,a lot of equilibrium ultrafine MgZn2 precipitates precipitate along dislocations because defects can provide the favorable conditions for the migration and segregation of solute atoms.     

Preface to the Special Issue on Semiconductor Optoelectronic Integrated Circuits

The past 20 years have witnessed the rapid growth of photonic integration circuits(PIC)technology,which has been warmly embraced by both academia and the industry.Powered by the advanced development in material growth,processing,and design capability,the PIC technology now covers multiple material platforms,including III–V(InP,GaAs),silicon,silica,lithium niobate on insulator(LNOI)polymer,etc.The integration level has evolved from a single functional device to thousands of components on-chip.The increase in the performance and the complexity of the PICs have become an energetic booster for communication and information technology.     

Layered Birnessite Cathode with a Displacement/Intercalation Mechanism for High-Performance Aqueous Zinc-Ion Batteries

Mn-based rechargeable aqueous zinc-ion batteries(ZIBs)are highly promising because of their high operating voltages,attractive energy densities,and eco-friendliness.However,the electrochemical performances of Mn-based cathodes usually suffer from their serious structure transformation upon charge/discharge cycling.Herein,we report a layered sodium-ion/crystal water co-intercalated Birnessite cathode with the formula of Na0.55Mn2O4·0.57H2O(NMOH)for high-performance aqueous ZIBs.A displacement/intercalation electrochemical mechanism was confirmed in the Mn-based cathode for the first time.Na+and crystal water enlarge the interlayer distance to enhance the insertion of Zn^2+,and some sodium ions are replaced with Zn^2+ in the first cycle to further stabilize the layered structure for subsequent reversible Zn^2+/H^+ insertion/extraction,resulting in exceptional specific capacities and satisfactory structural stabilities.Additionally,a pseudo-capacitance derived from the surface-adsorbed Na^+ also contributes to the electrochemical performances.The NMOH cathode not only delivers high reversible capacities of 389.8 and 87.1 mA h g^−1 at current densities of 200 and 1500 mA g^−1,respectively,but also maintains a good long-cycling performance of 201.6 mA h g^−1 at a high current density of 500 mA g^−1 after 400 cycles,which makes the NMOH cathode competitive for practical applications.     

A numerical simulation study of CO 2 injection for enhancing hydrocarbon recovery and sequestration in liquid-rich shales

Less than 10% of oil is usually recovered from liquid-rich shales and this leaves much room for improvement, while water injection into shale formation is virtually impossible because of the extremely low permeability of the formation matrix. Injecting carbon dioxide (CO₂) into oil shale formations can potentially improve oil recovery. Furthermore, the large surface area in organicrich shale could permanently store CO₂ without jeopardizing the formation integrity. This work is a mechanism study of evaluating the effectiveness of CO₂-enhanced oil shale recovery and shale formation CO₂ sequestration capacity using numerical simulation. Petrophysical and fluid properties similar to the Bakken Formation are used to set up the base model for simulation. Result shows that the CO₂ injection could increase the oil recovery factor from 7.4% to 53%. In addition, petrophysical characteristics such as in situ stress changes and presence of a natural fracture network in the shale formation are proven to have impacts on subsurface CO₂ flow. A response surface modeling approach was applied to investigate the interaction between parameters and generate a proxy model for optimizing oil recovery and CO₂ injectivity.