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.

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.

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.

Paleoenvironmental Evolution and Organic Matter Enrichment Genesis of the Late Turonian Black Shale in the Southern Songliao Basin,NE China

The Upper Cretaceous Qingshankou Formation black shales,deposited in the late Turonian(LTB shales),are the main source rocks of the Songliao Basin.The origins of organic matter enrichment of the shales is a contentious subject fuelling many ongoing debates.This study investigates the genesis of the organic matter-rich shale by using molecular geochemistry.The LTB shales can be divided into three sections.The SectionⅠshales were deposited in saline,stratified and anoxic water conditions,which are related to seawater incursion events.At least three episodic and periodic seawater incursion events were recognized during SectionⅠshale deposition.The SectionⅡshales deposited in brackish to fresh and deep lake-level conditions with high primary productivity,which are related to lake-level transgression.The SectionⅢshales were deposited under fresh and slightly oxidized water conditions,which are related to lake-level regression.Two organic matter enrichment models for the LTB shales are identified,that is,the seawater incursion model and the maximum lake-level transgression sedimentation model,which act on different shale sections,both playing significant roles in the enrichment of organic matter.

Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution

Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.

The formation and evolutionary characteristics of organic matter and pyrites in the continental shales of the 3^(rd)submember of Chang 7 Member,Yanchang formation,Ordos Basin,China

Through microscopic analyses(e.g.,organic macerals,thin section observation,scanning electron microscope(SEM)imaging of fresh bedding planes via argon ion milling,and energy spectrum tests)combined with Rock-Eval analyses,this study systematically investigated the organic matter and pyrites in the continental shales in the 3^(rd)submember of the Chang 7 Member(Chang 7^(3)submember)in the Yanchang Formation,Ordos Basin and determined their types and the formation and evolutionary characteristics.The results are as follows.The organic matter of the continental shales in the Chang 7^(3)submember is dominated by amorphous bituminites and migrabitumens,which have come into being since the early diagenetic stage and middle diagenetic stage A,respectively.The formation and transformation of organic matter is a prerequisite for the formation of pyrites.The Ordos Basin was a continental freshwater lacustrine basin and lacked sulphates in waters during the deposition of the Chang 7 Member.Therefore,the syndiagenetic stage did not witness the formation of large quantities of pyrites.Since the basin entered early diagenetic stage A,large quantities of sulfur ions were released as the primary organic matter got converted into bituminites and,accordingly,pyrites started to form.However,this stage featured poorer fluid and spatial conditions compared with the syndepositional stage due to withdraw of water,the partial formation of bituminites,and a certain degree of compaction.As a result,large quantities of pyrrhotite failed to transition into typical spherical framboidal pyrites but grew into euhedral monocrystal aggregates.In addition,pyrites are still visible in the migrabitumens in both microfractures and inorganic pores of mudstones and shales,indicating that the pyrite formation period can extend until the middle diagenetic stage A.

Industrial Organization in the Digital Economy Era:Evolution and Effects

Advances in digital technology and vast data applications have resulted in the emergence of the digital economy paradigm,which is a new techno-economic paradigm for the digital economy age.Under this paradigm,the industrial organization has shifted toward networked,platform-based,boundaryless,and integrated development with new characteristics.Specifically,there has been a fierce“positional arms race”fueled by financial capital,accelerating the growth of platform companies.The“hierarchical monopolistic competition”market structure has taken shape,resulting in a“coexistence without disruption”monopolistic competition.As platform businesses expand into new business sectors,competition among industrial ecosystems intensifies.Data and algorithms have become secret weapons for corporate success,allowing platform companies to expand their monopolistic forces.Industrial organization in the digital era has revolutionized the operating rules and logic of industrial economy,giving rise to new industries,business models,and paradigms,as well as being conducive to international cooperation and intelligent regulation.Meanwhile,it has introduced new challenges to socioeconomic development,making platform companies’anti-competitive and monopolistic behaviors more implicit,privacy and security concerns more conspicuous,and antitrust identification and investigation more difficult.The government should embrace the evolving trends of industrial organization in the digital economy era,accelerate regulatory transition,and strengthen governance and regulation under the digital economy paradigm.

Boosting photocatalytic hydrogen evolution enabled by SiO_(2)-supporting chiral covalent organic frameworks with parallel stacking sequence

Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.

Multifunctional catalytic sites regulation of atomic-scale iridium on orthorhombic-CoSe_(2)for high efficiency dual-functional alkaline hydrogen evolution and organic degradation

The earth-abundant and high-performance catalysts are crucial for commercial implementation of hydrogen evolution reaction(HER).Herein,a multifunctional site strategy to construct excellent HER catalysts by incorporating iridium(Ir)ions on the atomic scale into orthorhombic-CoSe2(Ir-CoSe_(2))was reported.Outstanding hydrogen evolution activity in alkaline media such as a low overpotential of 48.7 mV at a current density of 10 mA cm^(-2)and better performance than commercial Pt/C catalysts at high current densities were found in the Ir-CoSe_(2) samples.In the experiments and theoretical calculations,it was revealed that Ir enabled CoSe_(2)to form multifunctional sites to synergistically catalyze alkaline HER by promoting the adsorption and dissociation of H_(2)O(Ir sites)and optimizing the binding energy for H^(*)on Co sites.It was noticeable that the electrolytic system comprising the Ir-CoSe_(2)electrode not only produced hydrogen efficiently via HER,but also degraded organic pollutants(Methylene blue).The cell voltage of the dual-function electrolytic system was 1.58 V at the benchmark current density of 50 mA cm^(-2),which was significantly lower than the conventional water splitting voltage.It was indicated that this method was a novel strategy for designing advanced HER electrocatalysts by constructing multifunctional catalytic sites for hydrogen production and organic degradation.

Embryos - the evolutionary boundary of kingdoms of organisms

Bioevolution is still a main puzzle and attracts many scientists to research on it. Here I present that organisms have two impor- tant properties, definite structure and self-reproduction. Based on the number and connection of the structural units, organisms can be di- vided into three groups, unicellular, particellular and polycellular organisms. It can be called polycellular evolution that organisms evolve from unicellular, particellular to polycellular. Also it can be called diploid evolution that organisms evolve from haplobes to diplobes, two groups based on the reproductive differences. Some concepts like spore, zygote and embryos are redefined in the paper. Moreover, I present that embryos are the most important boundary of bioevolution and organisms can be divided into two evolutionary phases, the lower and the higher. The lower organisms, Kingdom Microbia (kingd. nov.), are inembryonate, which include Acytophyla (phyl. nov.), bacteria, protozoa, fungi and inembryonate algae. The higher organisms are embryonate and have two branches, Kingdom Plantae and Kingdom Animalia. Plantae are sessile and, autotrophic or sporogenic, which include higher plants and Nudembryophyta (phyl. nov.). Animalia are heterotrophic and, motile or gametogenic, which include all multicellular animals. The new system, which reflects the two important phases of bioevolu- tion and two branches of higher organisms, can really correct the problem of different kingdoms in different researches or by different re- searchers.

The Most Primitive Extant Ancestor of Organisms and Discovery of Definitive Evolutionary Equations Based on Complete Genome Structures

Evolutionary divergence has been characterized based on morphological and molecular features using rationale based on Darwin’s theory of natural selection. However, universal rules that govern genome evolution have not been identified. Here, a simple, innovative approach has been developed to evaluate biological evolution initiating the origin of life: whole genomes were divided into several fragments, and then differences in normalized nucleotide content between nucleotide pairs were compared. Intramolecular nucleotide differences in complete mitochondrial genomes reflect evolutionary divergence. The values of (G – C), (G – T), (G – A), (C – T), (C – A) and (T – A) reflect biological evolution, and these values except for (G – C) and (T – A) change inversely to positive from negative along biological evolution of bacterial genomes. More highly evolved organisms, such as primates and birds, seem to have greater levels of (C – T) in mitochondria. Based on nucleotide content structures, Monosiga brevicollis mitochondria may be the most primitive extant ancestor of the species examined here. The two normalized nucleotide contents are universally expressed by a linear regression line, (X – Y)/(X + Y) = a(X – Y) + b, where X and Y are nucleotide contents and (a) and (b) are constants. The value of (G + C), (G + A), (G + T), (C + A), (C + T) and (A + T) was ~0.5. Plotting (X – Y)/(X + Y) against X/Y showed a logarithmic function (X – Y)/(X + Y) = a lnX/Y + b, where (a) and (b) are constant. Nucleotide content changes are expressed by a definitive equation, (X – Y) ≈ 0.25 ln(X/Y).

Evolution of Self-Organized Ge Quantum Dots During Ultra High Vacuum Annealing

The evolution of self organized Ge quantum dots structure is investigated by scanning tunneling microscopy and atomic force microscopy during annealing treatment up to 700℃ in an ultra high vacuum(UHV) system.When the sample temperature rises to 630℃,a great amount of new dots emerge on the wetting layer,which are believed to be incoherent islands compared with the dislocation free coherent islands formed during molecular beam epitaxy growth.

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.

Mg/MgO interfaces as efficient hydrogen evolution cathodes causing accelerated corrosion of additive manufactured Mg alloys:A DFT analysis

The corrosion rates of additive-manufactured Mg alloys are higher than their as-cast counterparts,possibly due to increased kinetics for the hydrogen evolution reaction on secondary phases,which may include oxide inclusions.Scanning Kelvin Probe Force Microscopy demonstrated that MgO inclusions could act as cathodes for Mg corrosion,but their low conductivity likely precludes this.However,the density of state calculations through density functional theory using hybrid HSE06 functional revealed overlapping electronic states at the Mg/MgO interface,which facilitates electron transfers and participates in redox reactions.Subsequent determination of the hydrogen absorption energy at the Mg/MgO interface reveals it to be an excellent catalytic site,with HER being found to be a factor of 23x more efficient at the interface than on metallic Mg.The results not only support the plausibility of the Mg/MgO interface being an effective cathode to the adjacent anodic Mg matrix during corrosion but also contribute to the understanding of the enhanced cathodic activities observed during the anodic dissolution of magnesium.

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.

Valence electronic engineering of superhydrophilic Dy-evoked Ni-MOF outperforming RuO_(2) for highly efficient electrocatalytic oxygen evolution

Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.

Microwave shock motivating the Sr substitution of 2D porous GdFeO_(3) perovskite for highly active oxygen evolution

The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.

Optimizing 3d spin polarization of CoOOH by in situ Mo doping for efficient oxygen evolution reaction

Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will benefit their quick transition to the next catalysts.Herein,Mo-doped CoOOH was designed as a high-performance model electrocatalyst with durability for 20 h at 10 mAcm−2.Additionally,it had an overpotential of 260 mV(glassy carbon)or 215 mV(nickel foam),which was 78 mV lower than that of IrO_(2)(338 mV).In situ,Raman spectroscopy revealed the transformation process of CoOOH.Calculations using the density functional theory showed that during OER,doped Mo increased the spin-up density of states and shrank the spin-down bandgap of the 3d orbits in the reconstructed CoOOH under the electrochemical activation process,which simultaneously optimized the adsorption and electron conduction of oxygen-related intermediates on Co sites and lowered the OER overpotentials.Our research provides new insights into the methodical planning of the creation of transition-metal oxyhydroxide OER catalysts.