Highly mass activity electrocatalysts with ultralow Pt loading on carbon black for hydrogen evolution reaction

Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.

Boosting Oxygen Evolution Reaction Performance on NiFe‑Based Catalysts Through d‑Orbital Hybridization

Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.

Timescales of interface-coupled dissolution-precipitation reactions oncarbonates

In the Earth's upper crust, where aqueous fluids can circulate freely, most mineral transformations are controlled by the coupling between the dissolution of a mineral that releases chemical species into the fluid and precipitation of new minerals that contain some of the released species in their crystal structure, the coupled process being driven by a reduction of the total free-energy of the system. Such coupled dissolution-precipitation processes occur at the fluid-mineral interface where the chemical gradients are highest and heterogeneous nucleation can be promoted, therefore controlling the growth kinetics of the new minerals. Time-lapse nanoscale imaging using Atomic Force Microscopy(AFM) can monitor the whole coupled process under in situ conditions and allow identifying the time scales involved and the controlling parameters. We have performed a series of experiments on carbonate minerals(calcite, siderite, dolomite and magnesite) where dissolution of the carbonate and precipitation of a new mineral was imaged and followed through time. In the presence of various species in the reacting fluid(e. g. antimony, selenium, arsenic, phosphate), the calcium released during calcite dissolution binds with these species to form new minerals that sequester these hazardous species in the form of a stable solid phase. For siderite, the coupling involves the release of Fe^(2+) ions that subsequently become oxidized and then precipitate in the form of FeIIIoxyhydroxides. For dolomite and magnesite,dissolution in the presence of pure water(undersaturated with any possible phase) results in the immediate precipitation of hydrated Mg-carbonate phases. In all these systems, dissolution and precipitation are coupled and occur directly in a boundary layer at the carbonate surface. Scaling arguments demonstrate that the thickness of this boundary layer is controlled by the rate of carbonate dissolution,the equilibrium concentration of the precipitates and the kinetics of diffusion of species in a boundary layer. From these parameters a characteristic time scale and a characteristic length scale of the boundary layer can be derived. This boundary layer grows with time and never reaches a steady state thickness as long as dissolution of the carbonate is faster than precipitation of the new mineral. At ambient temperature, the surface reactions of these dissolving carbonates occur on time-scales of the order of seconds to minutes, indicating the rapid surface rearrangement of carbonates in the presence of aqueous fluids. As a consequence, many carbonate-fluid reactions in low temperature environments are controlled by local thermodynamic equilibria rather than by the global equilibrium in the whole system.

Effect of Addition Sequence during Neutralization and Precipitation on Iron-based Catalysts for High Temperature Shift Reaction

The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials during neutralization and precipitation was investigated. XRD, BET and particle size distribution （PSD） were used to characterize the prepared catalysts. It was found that the catalyst crystals were all γ-Fe2O3, and the intermediate of the catalyst after aging was Fe3O4. The crystallographic form of the catalyst and its intermediate was not affected by the addition sequence in the neutralization and precipitation process. The results showed that the specific surface area and the particle size of the catalysts depended on the addition sequence to the mother liquor. Cobalt with a small amount of copper and aluminum could increase the specific surface area and decrease the particle size of catalysts.

Discontinuous Precipitation Reaction Front of Cellular Recrystallization for a Single-Crystal Superalloy Studied by Electron Microscopy

Combining analytical transmission electron microscopy systematic tilting, scanning transmission electron microscopy mapping and nano-beam electron diffraction operations, we obtain direct experimental proofs on the boundary type, elemental distribution and structure of the cellular reerystallization reaction front for a single- crystal superalloy. It is demonstrated that the cellular recrystallization reaction front usually corresponds to coincidence site lattice boundaries, and a thin layer of γ-forming elements such as Re, Cr, Mo and Co invariably exists in the direct reaction front. Furthermore, the thin layer with γ-forming elements is proved to be γ phase, with the same orientation as the neighboring original matrix.

Lattice Boltzmann Simulation of a Gas-to-Solid Reaction and Precipitation Process in a Circular Tube

The lattice Boltzmann method(LBM)is used to simulate the growth of a solid-deposit on the walls of a circular tube resulting from a gas-to-solid reaction and precipitation process.This process is of particular interest for the design of reactors for the production of hydrogen by the heterogeneous hydrolysis of steam with Zn vapor in the Zn/ZnO thermochemical cycle.The solid deposit of ZnO product on the tube wall evolves in time according to the temporally-and axially-varying convective-diffusive transport and reaction of Zn vapor with steam on the solid surface.The LBM is wellsuited to solving problems with coupled flow,heat and mass transfer in a time-evolving domain.Here,a D2Q9 axisymmetric multiple-relaxation-time(MRT)lattice Boltzmann scheme is used to simulate incompressible fluid transport while a D2Q5 axisymmetric MRT lattice Boltzmann scheme is used to simulate the convective-diffusive transport of Zn vapor.The model is first validated against several analytical solutions,followed by a parametric study to understand the effect of Reynolds,Schmidt,and Damk?hler numbers on the time evolution of the ZnO deposition profile along the tube axis.The axial location of the fastest deposition is found to increase with increasing Peclet number,and decrease with increasing Damk?hler number,with no independent effect from the Schmidt number.When the reaction kinetics are assumed to increase along the tube axis due to nonisothermal tube wall temperature,a second peak in the deposition profile can be observed for sufficiently low values of Da/Pe.

Reaction视频中用户弹幕信息交互行为的情感反应生成机理研究

深入挖掘Reaction视频中弹幕信息交互行为的情感反应机理有助于理解用户弹幕创作背后的情感生成原因及情感变化过程。本文基于情感反应模型,利用定向内容分析法对哔哩哔哩网站中11个热门视频的弹幕信息资源、视频内容以及reactor反应情况展开编码研究,构建了Reaction视频中用户弹幕信息交互行为的情感反应生成机理模型。研究发现,Reaction视频弹幕信息交互行为中的情感反应生成机理总体上遵循“信息刺激-情感反应”的路径,信息刺激有时会独立唤醒情绪或特定情感态度,有时也会通过唤醒特定情感态度进而影响情绪或内化情感态度的生成。该模型有助于提升情感反应理论在计算机协助交流中的情境化探索,也将为社交媒体中用户与信息交互提供优化建议。

Kinetics of hydrogen peroxide-sulfur (IV) reaction in atmospheric precipitation

The kinetics of the reaction of dissolved S(IV) with H2O2 was studied on 59 precipitation samples collected in Southwestern China, during the period of June 1988 to October 1989, from which the oxidation rates of the reaction were measured. The extent of reaction was followed by continuous amperometric measurement of the concentrations of the reagents. The two systems (i. e. rainwater and purified water) have been studied with the same methodology under identical reaction conditions (e. g. reagent concentrations, ionic strength and temperature). The kinetics was studied in no buffer solutions. The effect of formaldehyde on the reaction has also been studied, including kinetic studies in laboratory and model calculations, and it is indicated that formaldehyde with typical atmospheric concentration exerts no influence on the reaction of dissolved S(IV) with H2O2. In addition, the activation energy of the reaction was also measured in purified water as reaction medium for temperature range 0-50℃ at pH 4.0.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Exciting lattice oxygen of nickel–iron bi-metal alkoxide for efficient electrochemical oxygen evolution reaction

High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.

Effect of drying-wetting cycles on pore characteristics and mechanical properties of enzyme-induced carbonate precipitation-reinforced sea sand

Enzyme-induced carbonate precipitation(EICP)is an emanating,eco-friendly and potentially sound technique that has presented promise in various geotechnical applications.However,the durability and microscopic characteristics of EICP-treated specimens against the impact of drying-wetting(D-W)cycles is under-explored yet.This study investigates the evolution of mechanical behavior and pore charac-teristics of EICP-treated sea sand subjected to D-W cycles.The uniaxial compressive strength(UCS)tests,synchrotron radiation micro-computed tomography(micro-CT),and three-dimensional(3D)recon-struction of CT images were performed to study the multiscale evolution characteristics of EICP-reinforced sea sand under the effect of D-W cycles.The potential correlations between microstructure characteristics and macro-mechanical property deterioration were investigated using gray relational analysis(GRA).Results showed that the UCS of EICP-treated specimens decreases by 63.7% after 15 D-W cycles.The proportion of mesopores gradually decreases whereas the proportion of macropores in-creases due to the exfoliated calcium carbonate with increasing number of D-W cycles.The micro-structure in EICP-reinforced sea sand was gradually disintegrated,resulting in increasing pore size and development of pore shape from ellipsoidal to columnar and branched.The gray relational degree suggested that the weight loss rate and UCS deterioration were attributed to the development of branched pores with a size of 100-1000 m m under the action of D-W cycles.Overall,the results in this study provide a useful guidancee for the long-term stability and evolution characteristics of EICP-reinforced sea sand under D-W weathering conditions.

Boric Acid-Assisted Pyrolysis for High-Loading Single-Atom Catalysts to Boost Oxygen Reduction Reaction in Zn-Air Batteries

The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Spatio-Temporal Characteristics of Heavy Precipitation Forecasts from ECMWF in Eastern China

This study examines the spatio-temporal characteristics of heavy precipitation forecasts in eastern China from the European Centre for Medium-Range Weather Forecasts(ECMWF) using the time-domain version of the Method for Object-based Diagnostic Evaluation(MODE-TD). A total of 23 heavy rainfall cases occurring between 2018 and 2021 are selected for analysis. Using Typhoon “Rumbia” as a case study, the paper illustrates how the MODE-TD method assesses the overall simulation capability of models for the life history of precipitation systems. The results of multiple tests with different parameter configurations reveal that the model underestimates the number of objects’ forecasted precipitation tracks, particularly at smaller radii. Additionally, the analysis based on centroid offset and area ratio tests for different classified precipitation objects indicates that the model performs better in predicting large-area, fast-moving, and longlifespan precipitation objects. Conversely, it tends to have less accurate predictions for small-area, slow-moving, and shortlifespan precipitation objects. In terms of temporal characteristics, the model overestimates the forecasted movement speed for precipitation objects with small-area, slow movement, or both long and short lifespans while underestimating it for precipitation with fast movement. In terms of temporal characteristics, the model tends to overestimate the forecasted movement speed for precipitation objects with small-area, slow movement, or both long and short lifespans while underestimating it for precipitation with fast movement. Overall, the model provides more accurate predictions for the duration and dissipation of precipitation objects with large-area or long-lifespan(such as typhoon precipitation) while having large prediction errors for precipitation objects with small-area or short-lifespan. Furthermore, the model’s simulation results regarding the generation of precipitation objects show that it performs relatively well in simulating the generation of large-area and fast-moving precipitation objects. However, there are significant differences in the forecasted generation of small-area and slow-moving precipitation objects after 9 hours.

Future changes in precipitation and water availability over the Tibetan Plateau projected by CMIP6 models constrained by climate sensitivity

Precipitation projections over the Tibetan Plateau(TP)show diversity among existing studies,partly due to model uncertainty.How to develop a reliable projection remains inconclusive.Here,based on the IPCC AR6–assessed likely range of equilibrium climate sensitivity(ECS)and the climatological precipitation performance,the authors constrain the CMIP6(phase 6 of the Coupled Model Intercomparison Project)model projection of summer precipitation and water availability over the TP.The best estimates of precipitation changes are 0.24,0.25,and 0.45 mm d^(−1)(5.9%,6.1%,and 11.2%)under the Shared Socioeconomic Pathway(SSP)scenarios of SSP1–2.6,SSP2–4.5,and SSP5–8.5 from 2050–2099 relative to 1965–2014,respectively.The corresponding constrained projections of water availability measured by precipitation minus evaporation(P–E)are 0.10,0.09,and 0.22 mm d^(−1)(5.7%,4.9%,and 13.2%),respectively.The increase of precipitation and P–E projected by the high-ECS models,whose ECS values are higher than the upper limit of the likely range,are about 1.7 times larger than those estimated by constrained projections.Spatially,there is a larger increase in precipitation and P–E over the eastern TP,while the western part shows a relatively weak difference in precipitation and a drier trend in P–E.The wetter TP projected by the high-ECS models resulted from both an approximately 1.2–1.4 times stronger hydrological sensitivity and additional warming of 0.6℃–1.2℃ under all three scenarios during 2050–2099.This study emphasizes that selecting climate models with climate sensitivity within the likely range is crucial to reducing the uncertainty in the projection of TP precipitation and water availability changes.

Assessment of Wet Season Precipitation in the Central United States by the Regional Climate Simulation of the WRFG Member in NARCCAP and Its Relationship with Large-Scale Circulation Biases

Assessment of past-climate simulations of regional climate models(RCMs)is important for understanding the reliability of RCMs when used to project future regional climate.Here,we assess the performance and discuss possible causes of biases in a WRF-based RCM with a grid spacing of 50 km,named WRFG,from the North American Regional Climate Change Assessment Program(NARCCAP)in simulating wet season precipitation over the Central United States for a period when observational data are available.The RCM reproduces key features of the precipitation distribution characteristics during late spring to early summer,although it tends to underestimate the magnitude of precipitation.This dry bias is partially due to the model’s lack of skill in simulating nocturnal precipitation related to the lack of eastward propagating convective systems in the simulation.Inaccuracy in reproducing large-scale circulation and environmental conditions is another contributing factor.The too weak simulated pressure gradient between the Rocky Mountains and the Gulf of Mexico results in weaker southerly winds in between,leading to a reduction of warm moist air transport from the Gulf to the Central Great Plains.The simulated low-level horizontal convergence fields are less favorable for upward motion than in the NARR and hence,for the development of moist convection as well.Therefore,a careful examination of an RCM’s deficiencies and the identification of the source of errors are important when using the RCM to project precipitation changes in future climate scenarios.

Impacts of Future Changes in Heavy Precipitation and Extreme Drought on the Economy over South China and Indochina

Heavy precipitation and extreme drought have caused severe economic losses over South China and Indochina(INCSC)in recent decades.Given the areas with large gross domestic product(GDP)in the INCSC region are distributed along the coastline and greatly affected by global warming,understanding the possible economic impacts induced by future changes in the maximum consecutive 5-day precipitation(RX5day)and the maximum consecutive dry days(CDD)is critical for adaptation planning in this region.Based on the latest data released by phase 6 of the Coupled Model Intercomparison Project(CMIP6),future projections of precipitation extremes with bias correction and their impacts on GDP over the INCSC region under the fossil-fueled development Shared Socioeconomic Pathway(SSP5-8.5)are investigated.Results indicate that RX5day will intensify robustly throughout the INCSC region,while CDD will lengthen in most regions under global warming.The changes in climate consistently dominate the effect on GDP over the INCSC region,rather than the change of GDP.If only considering the effect of climate change on GDP,the changes in precipitation extremes bring a larger impact on the economy in the future to the provinces of Hunan,Jiangxi,Fujian,Guangdong,and Hainan in South China,as well as the Malay Peninsula and southern Cambodia in Indochina.Thus,timely regional adaptation strategies are urgent for these regions.Moreover,from the sub-regional average viewpoint,over two thirds of CMIP6 models agree that maintaining a lower global warming level will reduce the economic impacts from heavy precipitation over the INCSC region.

Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.

Time-lagged Effects of the Spring Atmospheric Heat Source over the Tibetan Plateau on Summer Precipitation in Northeast China during 1961–2020:Role of Soil Moisture

The spring atmospheric heat source(AHS)over the Tibetan Plateau(TP)has been suggested to affect the Asian summer monsoon and summer precipitation over South China.However,its influence on the summer precipitation in Northeast China(NEC)remains unknown.The connection between spring TP AHS and subsequent summer precipitation over NEC from 1961 to 2020 is analyzed in this study.Results illustrate that stronger spring TP AHS can enhance subsequent summer NEC precipitation,and higher soil moisture in the Yellow River Valley-North China region(YRVNC)acts as a bridge.During spring,the strong TP AHS could strengthen the transportation of water vapor to East China and lead to excessive rainfall in the YRVNC.Thus,soil moisture increases,which regulates local thermal conditions by decreasing local surface skin temperature and sensible heat.Owing to the memory of soil moisture,the lower spring sensible heat over the YRVNC can last until mid-summer,decrease the land–sea thermal contrast,and weaken the southerly winds over the East Asia–western Pacific region and convective activities over the South China Sea and tropical western Pacific.This modulates the East Asia–Pacific teleconnection pattern,which leads to a cyclonic anomaly and excessive summer precipitation over NEC.