Rational construction of CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S S-scheme heterojunction photocatalyst for extraordinary photothermal-assisted photocatalytic H_(2) evolution

Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.

Efficient Solvothermal Synthesis of Defect-Rich Cu-BTC•MOF with Enhanced Electrocatalytic Activity in Alkaline Hydrogen Evolution Reaction

Porous metal–organic frameworks(MOFs) have been recently discovered to be efficient catalysts for energy applications and green technologies. Here, we report on a scalable catalytic platform using Cu–based MOFs for electrocatalytic alkaline hydrogen evolution reaction. First, the solvothermal synthesis of Cu–BTC MOFs(BTC = 1,3,5–benzenetricarboxylate) at 85 ℃ and a 1:60 ligand–to–solvent ratio allowed for minimizing the chemical consumption. Second, the obtained platform demonstrated enhanced electrochemical performance compared with commercially available Cu–based MOFs, with a potential of –230 versus –232 eV, logarithm of the current density of –3.6 versus –4.2 cm2, and electrochemical surface area of 75 versus 25 cm2per cm2of geometric area, respectively. Morphological and Raman analyses also revealed that the high concentration of defects in the obtained submicron Cu–BTC MOFs can contribute to their improved catalytic performance. Thus, our findings pave the way to the low–cost synthesis of energy–efficient MOF–based catalysts for hydrogen production.

Role of iron ore in enhancing gasification of iron coke:Structural evolution,influence mechanism and kinetic analysis

The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the microstructure of iron coke was investigated.Furthermore,a comparative study of the gasification reactions between iron coke and coke was conducted through non-isothermal thermogravimetric method.The findings indicate that compared to coke,iron coke exhibits an augmentation in micropores and specific surface area,and the micropores further extend and interconnect.This provides more adsorption sites for CO_(2) molecules during the gasification process,resulting in a reduction in the initial gasification temperature of iron coke.Accelerating the heating rate in non-isothermal gasification can enhance the reactivity of iron coke.The metallic iron reduced from iron ore is embedded in the carbon matrix,reducing the orderliness of the carbon structure,which is primarily responsible for the heightened reactivity of the carbon atoms.The kinetic study indicates that the random pore model can effectively represent the gasification process of iron coke due to its rich pore structure.Moreover,as the proportion of iron ore increases,the activation energy for the carbon gasification gradually decreases,from 246.2 kJ/mol for coke to 192.5 kJ/mol for iron coke 15wt%.

Catalyst–Support Interaction in Polyaniline‑Supported Ni_(3)Fe Oxide to Boost Oxygen Evolution Activities for Rechargeable Zn‑Air Batteries

Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.

Low‑Temperature Oxidation Induced Phase Evolution with Gradient Magnetic Heterointerfaces for Superior Electromagnetic Wave Absorption

Gradient magnetic heterointerfaces have injected infinite vitality in optimizing impedance matching,adjusting dielectric/magnetic resonance and promoting electromagnetic(EM)wave absorption,but still exist a significant challenging in regulating local phase evolution.Herein,accordion-shaped Co/Co_(3)O_(4)@N-doped carbon nanosheets(Co/Co_(3)O_(4)@NC)with gradient magnetic heterointerfaces have been fabricated via the cooperative high-temperature carbonization and lowtemperature oxidation process.The results indicate that the surface epitaxial growth of crystal Co_(3)O_(4) domains on local Co nanoparticles realizes the adjustment of magnetic-heteroatomic components,which are beneficial for optimizing impedance matching and interfacial polarization.Moreover,gradient magnetic heterointerfaces simultaneously realize magnetic coupling,and long-range magnetic diffraction.Specifically,the synthesized Co/Co_(3)O_(4)@NC absorbents display the strong electromagnetic wave attenuation capability of−53.5 dB at a thickness of 3.0 mm with an effective absorption bandwidth of 5.36 GHz,both are superior to those of single magnetic domains embedded in carbon matrix.This design concept provides us an inspiration in optimizing interfacial polarization,regulating magnetic coupling and promoting electromagnetic wave absorption.

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.

Microstructural evolution of AZ61 magnesium alloy predeformed by ECAE during semisolid isothermal treatment

The microstructural evolution of AZ61 magnesium alloy predeformed by equal channel angular extrusion（ECAE） during semisolid isothermal treatment（SSIT） was investigated by means of optical metalloscopy and image analysis equipment.The process involved application of ECAE to as-cast alloy at 310 ℃ to induce strain prior to heating in the semisolid region for different time lengths.The results show that extrusion pass,isothermal temperature and processing route have an influence on microstructural evolution of predeformed AZ61 magnesium alloy during SSIT.With the increase of extrusion pass,the solid particle size is reduced gradually.When isothermal temperature increases from 530 ℃ to 560 ℃,the average particle size increases from 22 μm to 35 μm.When isothermal temperature is 575 ℃,the average particle size decreases.The particle size of microstructure of AZ61 magnesium alloy predeformed by ECAE at BC during SSIT is the finest.

Formation and evolution of secondary minerals during bioleaching of chalcopyrite by thermoacidophilic Archaea Acidianus manzaensis

The formation and evolution of secondary minerals during bioleaching of chalcopyrite by thermoacidophilic Archaea Acidianus manzaensis were analyzed by combining synchrotron radiation X-ray diffraction（SR-XRD） and S, Fe and Cu Kα X-ray absorption near edge structure（XANES） spectroscopy. Leaching experiment showed that 82.4% of Cu2＋ was dissolved by A. manzaensis after 10 d. The surface of chalcopyrite was corroded apparently and covered with leaching products. During bioleaching, the formation and evolution of secondary minerals were as follows： 1） little elemental sulfur, jarosite, bornite and chalcocite were found at days 2 and 4; and 2） bornite and chalcocite disappeared, covellite formed, and jarosite gradually became the main component at days 6 and 10. These results indicated that metal-deficiency sulfides chalcocite and bornite were first formed with a low redox potential value（360-461 m V）, and then gradually transformed to covellite with a high redox potential value（461-531 m V）.

High quality Sb-doped SnO2 electrodes with high oxygen evolution potential prepared by in situ hydrothermal synthesis method

High quality Sb-doped SnO2 electrode, with high oxygen evolution potential of 3.0 V, was successfully synthesized on the Ti substrates by in situ hydrothermal synthesis method.

One-step hydrothermal synthesis of S-defect-controlled ZnIn_(2)S_(4) microflowers with improved kinetics process of charge-carriers for photocatalytic H_(2) evolution

Engineering lattice defects in two-dimensional(2 D) sulfide semiconductors has been accepted as an effective strategy to enhance the efficiency of the solar-to-fuels conversion.Although many researches have proven the lattice defect-mediated photocatalytic activity of ZnIn_(2)S_(4),the artificial control of Sdefects for optimizing the charge-carrier kinetics process in ZnIn_(2)S_(4) has long been a challenging task.Herein,we report a facile one-step method to modulate the lattice S-content of ZnIn_(2)S_(4) microflowers(MFs) only through adjusting the used amount of S-precursor in the hydrothermal solution that contains the metal precursors with a fixed Zn/In stoichiometric ratio at 1:2.We also demonstrated that the Svacancies at the In facets were the main type of lattice defects in the formed ZnIn_(2)S_(4) MFs,which could enhance both the separation and migration processes of the photoinduced charge-carriers due to the existence of discrete defect energy-levels(DELs) and the reduced effective mass of electrons,as evidenced by the first-principles calculations and the electron spectra analyses.The ZnIn_(2)S_(4) MFs with the optimal content of S-vacancy obtained by a hydrothermal treatment of the precursors with the Zn/In/S stoichiometric ratio of 1:2:8 possessed the long-lived photoinduced electron(~94.64 ns) for contributing to the photo-physical and-chemical processes.Thus,upon visible light irradiation,the H_(2)-evolution rate of this sample reached ~2.40 mmol h^(-1) g^(-1) with an apparent quantum efficiency of ~0.16% at 420 nm even though only using 5 mg of photocatalysts without any cocatalysts.

Responses of river bed evolution to flow-sediment process changes after Three Gorges Project in middle Yangtze River:A case study of Yaojian reach

The Three Gorges Project(TGP)has changed the flow-sediment process in the middle Yangtze River.For navigation purposes,there is an urgent need to study the changes of the river regime over a long-term period and the shoal-channel evolution over different seasons since the completion of the TGP.Based on analysis of the measured data and the results of a two-dimensional mathematical model,the changes of the river regime and river bed evolution in the Yaojian reach downstream of the TGP were studied.Results show that a high sediment transport flux helps to keep the main flow in the North Branch,while a low sediment transport flux helps to keep the main flow in the South Branch.Thus,the main branch will not change in the near future because of the low sediment transport load.In this study,the flow-sediment process adjusted by the TGP was restored to the conditions before the TGP,and the river bed evolution under the adjusted and non-adjusted flow-sediment conditions was calculated.After the completion of the TGP,the reservoir storage accelerated the flood recession process and decreased the erosion by 11.9%under the flow-sediment conditions in 2010,and the deposition in the flood season decreased by 56.4%.

Structural evolution of ZA27 alloy during semi-solid isothermal heat treatment

The structural evolution of ZA27 alloy modified by element Zr was studied during semi solid isothermal heat treatment, and its transformation mechanism was also discussed. The results indicate that the primary α phase changes from equiaxed grains to spherical grains gradually at semi solid temperature of 460 ℃. With increasing isothermal time, the eutectic between boundaries of α phase diffuses toward α phase, and the primary equiaxed grain arms merge and boundaries tend to disappear to form near particle grains. Further, the eutectic left on α boundaries melts to make the near particle grains separate, and form spherical structure at last. [

Environment friendly hydrothermal synthesis of carbon–Co3O4 nanorods composite as an efficient catalyst for oxygen evolution reaction

The design of cost-effective, highly active catalysts for hydrogen energy production is a vital element in the societal pursuit of sustainable energy. Water electrolysis is one of the most convenient processes to produce high purity hydrogen. Cobalt-based catalysts are well-known electrocatalysts for oxygen evolution reaction（OER）. In this article, all these merits indicate that the present cobalt nanocomposite is a promising electrocatalyst for OER. C–CoO-nanorods catalyst with nanorod structure was synthesized by hydrothermal treatment of CoCl·6HO/dextrose/urea mixture at 180 °C for 18 h and then calcined at400 °C for 3.5 h. The role of dextrose percentage in solution to achieve the uniform coating of carbon on the surface of CoO-nanorods has been demonstrated. The prepared materials were characterized by X-ray diffraction（XRD）, X-ray photoelectron spectrum（XPS）, field emission scanning electron microscopy（FE-SEM）, high-resolution transmission electron microscopy（HR-TEM）, and Brunauer–Emmett–Teller instrument（BET）. Due to its unique morphology, the C–CoO-nanorods catalyst exhibited better activity than CoO-microplates catalyst for OER in 1 M KOH aqueous solution. The results showed a highly efficient, scalable, and low-cost method for developing highly active and stable OER electrocatalysts in alkaline solution.

Effects of trace Cr on as-cast microstructure and microstructural evolution of semi-solid isothermal heat treatment ZC61 magnesium alloy

The content and kind of trace elements in magnesium alloys have important effects on their ascast and semi-solid microstructures. In this research work, effects of trace Cr on as-cast and semi-solid microstructures of ZC61 magnesium alloy were investigated by metal mold casting and semi-solid isothermal heat treatment. The results show that the addition of Cr can refine the α-Mg phase without generating a new phase, noticeably change the eutectic phase, and decrease the average size of solid particles at the same isothermal heat treatment conditions. Non-dendritic microstructures of all alloys are constituted of α_1-Mg phases, α_2-Mg phases and eutectic phases after water quenching. With isothermal temperature increased or holding time prolonged, the eutectic microstructure(α-Mg+MgZn_2+CuMgZn) at the grain boundaries in as-cast alloy is melted preferentially and then turned into semi-solid non-dendritic microstructure by processes of initial coarsening, microstructure separation, spheroidizing and final coarsening. Especially when the ZC61-0.1 Cr alloy was treated at 585 ℃ for 30 min, the ideal non-dendritic microstructure can be obtained, and the corresponding solid particle size and shape factor were 37.5 μm and 1.33, respectively. The coarsening process of solid α-Mg phase at higher temperature or longer time, which is affected by both combining growth and Ostwald ripening mechanism, is refrained when Cr is added to the ZC61 alloy.

Microstructure evolution of semi-solid Mg-14Al-0.5Mn alloys during isothermal heat treatment

A new Mg-14Al-0.5Mn alloy that exhibits a wide solidification range and sufficient fluidity for semi-solid forming was designed. And the rnicrostructure evolution of semi-solid Mg-14Al-0.5Mn alloy during isothermal heat treatment was investigated. The mechanism of the microstructure evolution and the processing conditions for isothermal heat treatment were also discussed. The results show that the microstructures of cast alloys consist of α-Mg,β-Mg17Al12 and a small amount of Al-Mn compounds. After holding at 520 ℃ for 3 min, the phases of β-Mg17Al12 and eutectic mixtures in the Mg-14Al-0.5Mn alloy melt and the microstructures of α-Mg change from developed dendrites to irregular solid particles. With increasing the isothermal time, the amount of liquid increases, and the solid particles grow large and become spherical. When the holding time lasts for 20 min or even longer, the solid and liquid phases achieve a state of dynamic equilibrium.

Cu-state evolution during leaching of bornite at 50 ℃

The bioleaching of bornite with mixed moderately thermophilic culture at 50 °C was investigated. The intermediary species formed during the leaching of bornite were characterized by XRD and XPS. In addition, the evolution of Cu-state during leaching of bornite was further studied by applying φh–p H diagram and cyclic voltammetry. The results showed that the bornite was more likely to be leached at high redox potential. Furthermore, the intermediary sulfides, such as isocubanite, covellite, chalcopyrite, disulfide, and polysulfide, were formed in the course of bornite dissolution. The Cu 2 p photoelectron spectrum revealed that the valence of copper in bornite and intermediary sulfide formed in the dissolution of bornite is ＋1. The bornite and chalcopyrite can be converted into each other, and both can be further converted to covellite and/or chalcocite.

Beach Morphology and Coastline Evolution in the Southern Bohai Strait

The beach studied in this paper spans a length of 51 km and is one of several long sandy beaches in the southern Bohai Strait. Due to the obstruction of islands in the northeast and the influence of the underwater topography, the wave environment in the offshore area is complex; beach types and sediment transport characteristics vary along different coasts. The coastlines extracted from six aerial photographs in different years were compared to demonstrate the evolving features. Seven typical beach profiles were selected to study the lateral beach variation characteristics. Continuous wind and wave observation data from Beihuangcheng ocean station during 2009 were employed for the hindcast of the local wave environment using a regional spectral wave model. Then the results of the wave hindcast were incorporated into the LITDRIFT model to compute the sediment transport rates and directions along the coasts and analyze the longshore sand movement. The results show that the coastline evolution of sand beaches in the southern Bohai Strait has spatial and temporal variations and the coast can be divided into four typical regions. Region （1）, the north coast of Qimudao, is a slightly eroded and dissipative beach with a large sediment transport rate; Region （II）, the southwest coast of Gangluan Port, is a slightly deposited and dissipative beach with moderate sediment transport rate; Region （III）, in the central area, is a beach that is gradually transformed from a slightly eroded dissipative beach to a moderately or slightly strong eroded bar-trough beach from west to east with a relatively moderate sediment transport rate. Region （IV）, on the east coast, is a strongly eroded and reflective beach with a weak sediment transport rate. The wave conditions exhibit an increasing trend from west to east in the off- shore area. The distribution of the wave-induced current inside the wave breaking region and the littoral sediment transport in the nearshore region exhibit a gradual weakening tendency from west to east, which is opposite to the trend of the wave conditions out- side the breaking region. The presence of submerged shoal （Dengzhou Shoal）, deep trough （Dengzhou Channel）, islands and irregu- lar topography influnces the wave climate, beach types, wave-induced current features, littoral sediment transport trends and coast- line evolution patterns in the southern Bohai Strait. Human activities, such as the sand exploitation of Dengzhou Shoal and other coastal engineering projects, also influence the beach morphology and coastline evolution.

Microstructural evolution of Mg9AlZnY alloy with vibration in lost foam casting during semi-solid isothermal heat treatment

The nearly equiaxed grains of Mg9AlZnY alloy were obtained by vibrating solidification in lost foam casting(LFC) and the microstructure of Mg9AlZnY alloy was analyzed.On this basis,the morphology and size of α-Mg grains fabricated by semi-solid isothermal heat treatment(SSIT) at 530 ℃ and 570 ℃ holding different time were studied.The results show that the main constituent phases of Mg9AlZnY alloy are α-Mg,β-Mg17Al12 and Al2Y,and the Y can greatly refine α-Mg grains.The distribution of α-Mg grains equivalent diameters between 20 and 100 μm is up to 87%,and the average roundness of α-Mg grains reaches 1.37 in the specimen obtained at 570 ℃ and holding time 60 min.According to the analysis of solidification kinetics and thermodynamic,binary eutectic with low melting point melts firstly on SSIT process.As the liquid fraction increases with the solute diffusibility,both of the shape and size of α-Mg grains change ceaselessly.When the liquid fraction reaches equilibrium,the α-Mg grains are gradually spheroidized under the interfacial tension,and then the α-Mg grains begin to combine and grow.Evolution of α-Mg dendritic grains on SSIT process is obviously different from that of equiaxed grains.

EDTA-assisted hydrothermal synthesis of flower-like CoSe_2 nanorods as an efficient electrocatalyst for the hydrogen evolution reaction

Hydrogen evolution reaction(HER) is a prospective method to generate pure hydrogen. The development of superior electrocatalysts based on earth-abundant materials, plays a critical role in the future.CoSe_2, one of the earth-abundant electrocatalysts, has been proved to be a promising catalyst for hydrogen generation. In our work, flower-like CoSe_2 nanorods with high quality are successfully synthesized through a facile ethylenediaminetetraacetic acid ligand(EDTA)-assisted hydrothermal process. The flower-like CoSe_2 nanorods show the brilliant electrochemical HER performance with 100 mA cm^(-2) at overpotential of 273 m V, a small Tafel slope of 35 mV dec^(-1) and strong durability in acid solution. The sparkly HER catalytic activity of CoSe_2 can be ascribed to its particular structure with large surface area and abundant active sites. Therefore, this work offers an outstanding candidate for improving hydrogen production capabilities by water electrolysis.