Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

New Rural Community Construction or Retention Development:A Comparative Analysis of Rural Settlement Transition Mechanism in Plain Agriculture Area of China Based on Actor Network Theory

It is an important way to realize rural revitalization and sustainable development to guide rural settlement transition(RST)in an appropriate way.This paper uses actor network theory(ANT)to construct a theoretical framework for the study of RST.Taking two typical villages with different transition paths in rural areas of North China Plain as examples,this paper reveals the mechanism of RST and makes a comparative analysis.The results show that:1)after identifying problems and obligatory passage point,key actors recruit heterogeneous actors into the actor network by entrusting them with common interests,and realize RST under the system operation.2)Rural settlements under different transition paths have similarities in the problems to be solved,collective actions and policy factors,but there are differences in the transition process,mechanism and effect.The actor network and mechanism of RST through the path of new rural community construction are more complex and the transition effect is more thorough.In contrast,the degree of RST of retention development path is limited if there is no resource and location advantage.3)Based on the applicable conditions of different paths,this paper designs a logical framework of‘Situation-Structure-Behavior-Result’to scientifically guide the identification of RST paths under the background of rural revitalization.

Photodoping-Modified Charge Density Wave Phase Transition in WS_(2)/1T-TaS_(2) Heterostructure

Controlling collective electronic states hold great promise for development of innovative devices. Here, we experimentally detect the modification of the charge density wave(CDW) phase transition within a 1T-TaS_(2) layer in a WS_(2)/1T-TaS_(2) heterostructure using time-resolved ultrafast spectroscopy. Laser-induced charge transfer doping strongly suppresses the commensurate CDW phase, which results in a significant decrease in both the phase transition temperature(T_(c)) and phase transition stiffness. We interpret the phenomenon that photoinduced hole doping, when surpassing a critical threshold value of ~ 10^(18)cm^(-3), sharply decreases the phase transition energy barrier. Our results provide new insights into controlling the CDW phase transition, paving the way for optical-controlled novel devices based on CDW materials.

Unveiling the pressure-driven metal–semiconductor–metal transition in the doped TiS_(2)

Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_12_12_1.Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.

Ultrafast Carrier Dynamics in Ba_(6)Cr_(2)S_(10)Modified by Toroidal Magnetic Phase Transition

Ba_(6)Cr_(2)S_(10)is a recently discovered magnetic material,in which the spins are aligned ferromagnetically in the ab-plane and anti-parallelly in a paired form along the c-axis.It is characterized as a quasi-one dimensional(1D)dimerized structure with a ferrotoroidic order,forming the simplest candidate toroidal magnetic(TM)order and exhibiting an anti-ferromagnetic-like transition at around 10 K.Time-resolved ultrafast dynamics investigation of the novel A-Cr-S(A:metal elements)family of quantum materials has rarely been reported.Here,we investigate the time-resolved pump-probe ultrafast dynamics of a Ba6Cr2S10 single crystal.A prominent change in the photo-excited carrier dynamics is observed at T_(c)=10 K,corresponding to the reported TM-paramagnetic phase transition.A potential unknown magnetic transition is also found at T^(*)=29 K.Our results provide new evidence for the TM magnetic transition in Ba_(6)Cr_(2)S_(10),and shed light on phase transitions in TM quantum materials.

Publisher Correction to:Strongly Coupled 2D Transition Metal Chalcogenide‑MXene‑Carbonaceous Nanoribbon Heterostructures with Ultrafast Ion Transport for Boosting Sodium/Potassium Ions Storage

Due to the technical fault,a wrong version of the paper was uploaded.The content of the article was not affected,but the layout of the article was affected.The original article has been corrected.

Advancing neuroscience through real-time processing of big data:Transition from open-loop to closed-loop paradigms

The brain functions as a closed-loop system that continuously generates behavior in response to the external environment and adjusts actions based on the outcomes.Traditional research methodologies in neuroscience,especially those employed in brain imaging experiments,have mainly adopted an open-loop paradigm(Grosenick et al.,2015).Functional neural circuits are analyzed offline and subsequently tested through manipulation of neuronal activities within specific regions or with genetic markers.By establishing a closed-loop research paradigm,functional ensembles can be detected and tested in real time with temporal sequences.These functional ensembles,rather than brain regions or genetically labeled neural populations,serve as fundamental units of neural networks,offering valuable insights into the dissection of neural circuits.The closed-loop research paradigm also enables the capture of high-dimensional activities of internal brain dynamics and precise elucidation of physiological processes such as learning,decision-making,and sleep.

Dissipation-Driven Superradiant Phase Transition of a Two-Dimensional Bose-Einstein Condensate in a Double Cavity

We study superradiant phase transitions in a hybrid system of a two-dimensional Bose–Einstein condensate of atoms and two cavities arranged with a tilt angle.By adjusting the loss rate of cavities,we map out the phase diagram of steady states within a mean field framework.It is found that when the loss rates of the two cavities are different,superradiant transitions may not occur at the same time in the two cavities.A first-order phase transition is observed between the states with only one cavity in superradiance and both in superradiance.In the case that both cavities are superradiant,a net photon current is observed flowing from the cavity with small decay rate to the one with large decay rate.The photon current shows a non-monotonic dependence on the loss rate difference,owing to the competition of photon number difference and cavity field phase difference.Our findings can be realized and detected in experiments.

Evolution of Superconducting-Transition Temperature with Superfluid Density and Conductivity in Pressurized Cuprate Superconductors

What factors fundamentally determine the value of superconducting transition temperature Tc in high temperature superconductors has been the subject of intense debate.Following the establishment of an empirical law known as Homes'law,there is a growing consensus in the community that the Tc value of the cuprate superconductors is closely linked to the superfluid density(ρ_(s))of its ground state and the conductivity(σ)of its normal state.However,all the data supporting this empirical law(ρ_(s)=AσT_(c))have been obtained from the ambientpressure superconductors.In this study,we present the first high-pressure results about the connection of the quantities of ρ_(s) and σ with T_(c),through the studies on the Bi_(1.74)Pb_(0.38)Sr_(1.88)CuO_(6+δ)and Bi_(2)Sr_(2)CaCu_(2)O_(8+δ),in which the value of their high-pressure resistivity(ρ=1/σ)is achieved by adopting our newly established method,while the quantity ofρs is extracted using Homes'law.We highlight that the Tc values are strongly linked to the joint response factors of magnetic field and electric field,i.e.,ρ_(s) and σ,respectively,implying that the physics determining T_(c) is governed by the intrinsic electromagnetic fields of the system.

Pressure-induced magnetic phase and structural transition in SmSb_(2)

Motivated by the recent discovery of unconventional superconductivity around a magnetic quantum critical point in pressurized CeSb_(2),here we present a high-pressure study of an isostructural antiferromagnetic(AFM) SmSb_(2) through electrical transport and synchrotron x-ray diffraction measurements.At P_C~2.5 GPa,we found a pressure-induced magnetic phase transition accompanied by a Cmca→P4/nmm structural phase transition.In the pristine AFM phase below P_C,the AFM transition temperature of SmSb_(2) is insensitive to pressure;in the emergent magnetic phase above P_C,however,the magnetic critical temperature increases rapidly with increasing pressure.In addition,at ambient pressure,the magnetoresistivity(MR) of SmSb_(2) increases suddenly upon cooling below the AFM transition temperature and presents linear nonsaturating behavior under high field at 2 K.With increasing pressure above P_C,the MR behavior remains similar to that observed at ambient pressure,both in terms of temperature-and field-dependent MR.This leads us to argue an AFM-like state for SmSb_(2) above P_C.Within the investigated pressure of up to 45.3 GPa and the temperature of down to 1.8 K,we found no signature of superconductivity in SmSb_(2).

Significantly enhanced thermal stability of HMX by phase-transition lysozyme coating

A new robust bio-inspired route by using lysozyme aqueous solution for surface modification on 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)was described in this paper.HMX crystals were coated by in situ phase transition of lysozyme(PTL)molecules.The HMX decorated by PTL was characterized by SEM,XRD,FTIR and XPS,demonstrating a dense core-shell coating layer.The coverage of lysozyme on HMX crystal was calculated by the ratio of sulfur content.The surface coverage increased from 60.5% to 93.5% when the content of PTL was changed from 0.5 wt% to 2.0 wt%,indicating efficient coating.The thermal stability of HMX was investigated by in situ XRD and DSC.The thermal phase transition temperature of HMX(β to δ phase)was delayed by 42℃ with 2.0 wt% PTL coating,which prevented HMX from thermal damage and sensitivity by the effect of PTL coating.After heating at 215℃,large cracks appeared in the naked HMX crystal,while the PTL coated HMX still maintained intact,with the impact energy of HMX dropped dramatically from 5 J to 2 J.However,the impact energy of HMX with 1.0 wt% and 2.0 wt% coating content(HMX@PTL-1.0 and HMX@PTL-2.0)was unchanged(5 J).Present results potentially enable large-scale fabrication of polymorphic energetic materials with outstanding thermal stability by novel lysozyme coating.

Temperature-sensing array using the metal-to-insulator transition of Nd_(x)Sm_(1-x)NiO_(3)

Rare-earth nickelates(RENiO_(3))show widely tunable metal-to-insulator transition(MIT)properties with ignorable variations in lattice constants and small latent heat across the critical temperature(TMIT).Particularly,it is worth noting that compared with the more commonly investigated vanadium oxides,the MIT of RENiO_(3)is less abrupt but usually across a wider range of temperatures.This sheds light on their alternative applications as negative temperature coefficient resistance(NTCR)thermistors with high sensitivity compared with the current NTCR thermistors,other than their expected use as critical temperature resistance thermistors.In this work,we demonstrate the NTCR thermistor functionality for using the adjustable MIT of Nd_(x)Sm_(1-x)NiO_(3)within 200–400 K,which displays larger magnitudes of NTCR(e.g.,more than 7%/K)that is unattainable in traditional NTCR thermistor materials.The temperature dependence of resistance(R–T)shows sharp variation during the MIT of Nd_(x)Sm_(1-x)NiO_(3)with no hysteresis via decreasing the Nd content(e.g.,x≤0.8),and such a R–T tendency can be linearized by introducing an optimum parallel resistor.The sensitive range of temperature can be further extended to 210–360 K by combining a series of Nd_(x)Sm_(1-x)NiO_(3)with eight rare-earth co-occupation ratios as an array,with a high magnitude of NTCR(e.g.,7%–14%/K)covering the entire range of temperatures.

Metal-to-insulator transitions in 3d-band correlated oxides containing Fe compositions

Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.

Repeated inoculation with rumen fluid accelerates the rumen bacterial transition with no benefit on production performance in postpartum Holstein dairy cows

Background The dairy cow’s postpartum period is characterized by dramatic physiological changes,therefore imposing severe challenges on the animal for maintaining health and milk output.The dynamics of the ruminal microbiota are also tremendous and may play a crucial role in lactation launch.We aim to investigate the potential benefits of early microbial intervention by fresh rumen microbiota transplantation(RMT)and sterile RMT in postpartum dairy cows.Twelve fistulated peak-lactation dairy cows were selected to be the donors for rumen fluid collection.Thirty postpartum cows were divided into 3 groups as the transplantation receptors respectively receiving 10 L fresh rumen fluid(FR),10 L sterile rumen fluid(SR),or 10 L saline(CON)during 3 d after calving.Results Production performance,plasma indices,plasma lipidome,ruminal microbiome,and liver transcriptome were recorded.After fresh and sterile RMT,we found that the molar proportion of propionic acid was increased on d 7 in the FR and SR groups and the bacterial composition was also significantly changed when compared with the CON group.A similarity analysis showed that the similarities between the CON group and FR or SR group on d 7 were 48.40%or 47.85%,whereas the similarities between microbiota on d 7 and 21 in the FR and SR groups were 68.34%or 66.85%.Dry matter intake and feed efficiency were not affected by treatments.Plasmaβ-hydroxybutyrate concentration in the FR group was decreased and significantly different lipids mainly included phosphatidylcholine and lysophosphatidylcholine containing polyunsaturated fatty acids.Hepatic transcriptomics analysis indicated acutephase response pathways were upregulated in the SR group.Conclusions Our study suggests that RMT can shorten the transition process of the ruminal microbiota of postpartum dairy cows with no benefit on dry matter intake or feed efficiency.Inoculation with rumen fluid may not be a useful approach to promote the recovery of postpartum dairy cows.

5-Fluorouracil dose escalation generated desensitized colorectal cancer cells with reduced expression of protein methyltransferases and no epithelial-to-mesenchymal transition potential

Background:Colorectal cancer(CRC)is one of the most frequently diagnosed cancers.In many cases,the poor prognosis of advanced CRC is associated with resistance to treatment with chemotherapeutic drugs such as 5-Fluorouracil(5-FU).The epithelial-to-mesenchymal transition(EMT)and dysregulation in protein methylation are two mechanisms associated with chemoresistance in many cancers.This study looked into the effect of 5-FU dose escalation on EMT and protein methylation in CRC.Materials and Methods:HCT-116,Caco-2,and DLD-1 CRC cell lines were exposed to dose escalation treatment of 5-FU.The motility and invasive potentials of the cells before and after treatment with 5-FU were investigated through wound healing and invasion assays.This was followed by aWestern blot which analyzed the protein expressions of the epithelial marker E-cadherin,mesenchymal marker vimentin,and the EMT transcription factor(EMTTF),the snail family transcriptional repressor 1(Snail)in the parental and desensitized cells.Western blotting was also conducted to study the protein expressions of the protein methyltransferases(PMTs),Euchromatic histone lysine methyltransferase 2(EHMT2/G9A),protein arginine methyltransferase(PRMT5),and SET domain containing 7/9(SETD7/9)along with the global lysine and arginine methylation profiles.Results:The dose escalation method generated 5-FU desensitized CRC cells with distinct morphological features and increased tolerance to high doses of 5-FU.The 5-FU desensitized cells experienced a decrease in migration and invasion when compared to the parental cells.This was reflected in the observed reduction in E-cadherin,vimentin,and Snail in the desensitized cell lines.Additionally,the protein expressions of EHMT2/G9A,PRMT5,and SETD7/9 also decreased in the desensitized cells and global protein lysine and arginine methylation became dysregulated with 5-FU treatment.Conclusion:This study showed that continuous,dose-escalation treatment of 5-FU in CRC cells generated 5-FU desensitized cancer cells that seemed to be less aggressive than parental cells.

Triple points and phase transitions of D-dimensional dyonic Ad S black holes with quasitopological electromagnetism in Einstein–Gauss–Bonnet gravity

By considering the negative cosmological constant Λ as a thermodynamic pressure, we study the thermodynamics and phase transitions of the D-dimensional dyonic Ad S black holes(BHs) with quasitopological electromagnetism in Einstein–Gauss–Bonnet(EGB) gravity. The results indicate that the small/large BH phase transition that is similar to the van der Waals(vdW) liquid/gas phase transition always exists for any spacetime dimensions. Interestingly, we then find that this BH system exhibits a more complex phase structure in 6-dimensional case that is missed in other dimensions.Specifically, it shows for D = 6 that we observed the small/intermediate/large BH phase transitions in a specific parameter region with the triple point naturally appeared. Moreover, when the magnetic charge turned off, we still observed the small/intermediate/large BH phase transitions and triple point only in 6-dimensional spacetime, which is consistent with the previous results. However, for the dyonic Ad S BHs with quasitopological electromagnetism in Einstein–Born–Infeld(EBI) gravity, the novel phase structure composed of two separate coexistence curves observed by Li et al. [Phys. Rev. D105 104048(2022)] disappeared in EGB gravity. This implies that this novel phase structure is closely related to gravity theories, and seems to have nothing to do with the effect of quasitopological electromagnetism. In addition, it is also true that the critical exponents calculated near the critical points possess identical values as mean field theory. Finally, we conclude that these findings shall provide some deep insights into the intriguing thermodynamic properties of the dyonic Ad S BHs with quasitopological electromagnetism in EGB gravity.

Comparative study on phase transition behaviors of fractional molecular field theory and random-site Ising model

Fractional molecular field theory(FMFT)is a phenomenological theory that describes phase transitions in crystals with randomly distributed components,such as the relaxor-ferroelectrics and spin glasses.In order to verify the feasibility of this theory,this paper fits it to the Monte Carlo simulations of specific heat and susceptibility versus temperature of two-dimensional(2D)random-site Ising model(2D-RSIM).The results indicate that the FMFT deviates from the 2D-RSIM significantly.The main reason for the deviation is that the 2D-RSIM is a typical system of component random distribution,where the real order parameter is spatially heterogeneous and has no symmetry of space translation,but the basic assumption of FMFT means that the parameter is spatially uniform and has symmetry of space translation.

Recent advances in transition metal phosphide materials:Synthesis and applications in supercapacitors

Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.

Catalytic Effect of Transition Metal Complexes of Triaminoguanidine on the Thermolysis of Energetic NC/DEGDN Composite

The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.

Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications

Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.