Strong metal‐support interaction boosting the catalytic activity of Au/TiO_(2) in chemoselective hydrogenation

Gold catalysts have been reported as highly effective catalysts in various oxidation reactions.However,for chemoselective hydrogenation reactions,gold‐based catalysts normally show much lowercatalytic activity than platinum group metals,even though their selectivities are excellent.Here,wereport that the chemoselective hydrogenation activity of 3‐nitrostyrene to 3‐vinylaniline overAu/TiO_(2)can be enhanced up to 3.3 times through the hydrogen reduction strategy.It is revealedthat strong metal‐support interaction,between gold nanoparticles(NPs)and TiO_(2)support,is introducedthrough hydrogen reduction,resulting in partial dispersion of reduced TiOx on the Au surface.The partially covered Au not only increases the perimeter of the interface between the gold NPs andthe support,but also benefits H_(2)activation.Reaction kinetic analysis and H_(2)‐D2 exchange reactionshow that H_(2)activation is the critical step in the hydrogenation of 3‐nitrostyrene to 3‐vinylaniline.Density functional theory calculations verify that hydrogen dissociation and hydrogen transfer arefavored at the interface of gold NPs and TiO_(2)over the hydrogen‐reduced Au/TiO_(2).This study providesinsights for fabricating highly active gold‐based catalysts for chemoselective hydrogenationreactions.

A general synthetic strategy for N, P co-doped graphene supported metal-rich noble metal phosphides for hydrogen generation

The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.

Recent advances in regulating the performance of acid oxygen reduction reaction on carbon-supported non-precious metal single atom catalysts

Developing high performance and low-cost catalysts for oxygen reduction reaction(ORR)in challenging acid condition is vital for proton-exchange-membrane fuel cells(PEMFCs).Carbon-supported nonprecious metal single atom catalysts(SACs)have been identified as potential catalysts in the field.Great advance has been obtained in constructing diverse active sites of SACs for improving the performance and understanding the fundamental principles of regulating acid ORR performance.However,the ORR performance of SACs is still unsatisfactory.Importantly,microenvironment adjustment of SACs offers chance to promote the performance of acid ORR.In this review,acid ORR mechanism,attenuation mechanism and performance improvement strategies of SACs are presented.The strategies for promoting ORR activity of SACs include the adjustment of center metal and its microenvironment.The relationship of ORR performance and structure is discussed with the help of advanced experimental investigations and theoretical calculations,which will offer helpful direction for designing advanced SACs for ORR.

Endeavors on the development of efficient and sustainable supported metal catalysts for chemical synthesis on solid-liquid interfaces

Supported metal catalysts,particularly for precious metals,have gained increasing attention in green synthetic chemistry.They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue,as well as reusability of the high-cost catalysts.Although great effort has been spent,the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable recyclable catalysts remains challenging.This highlight reveals a“molecular fence”metal stabilization strategy and discloses the metal evolution in Pd-catalyzed C-C bond formation reactions using Nheterocyclic carbene(NHC)-functionalized hypercrosslinked polymer support,wherein the polymeric skeleton isolates or confines the metal species involved in the catalytic reactions,and NHC captures free low-valent metal species in solution and stabilizes them on the support via strong metal-support coordination interaction.This strategy creates a novel route for the development of supported metal catalysts with high stability and provides insights into the reaction mechanism of heterogeneous catalysis.

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.

Towards advanced zinc anodes by interfacial modification strategies for efficient aqueous zinc metal batteries

Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.

Oxygen functionalization-assisted anionic exchange toward unique construction of flower-like transition metal chalcogenide embedded carbon fabric for ultra-long life flexible energy storage and conversion

The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storage and conversion application.The NiCCZ was then oxygen functionalized,facilitating the next step of stoichiometric sulfur anion diffusion during hydrothermal sulfurization,generating a flower-like metal hydroxysulfide structure(NiCCZOS)with strong partial implantation inside CC.Thus obtained NiCCZOS shows an excellent capacity when tested as a supercapacitor electrode in a three-electrode configuration.Moreover,when paired with the biomass-derived nitrogen-rich activated carbon,the asymmetric supercapacitor device shows almost 100%capacity retention even after 45,000 charge–discharge cycles with remarkable energy density(59.4 Wh kg^(-1)/263.8μWh cm^(–2))owing to a uniquely designed cathode.Furthermore,the same electrode performed as an excellent bifunctional water-splitting electrocatalyst with an overpotential of 271 mV for oxygen evolution reaction(OER)and 168.4 mV for hydrogen evolution reaction(HER)at 10 mA cm−2 current density along with 30 h of unhinged chronopotentiometric stability performance for both HER and OER.Hence,a unique metal chalcogenide composite electrode/substrate configuration has been proposed as a highly stable electrode material for flexible energy storage and conversion applications.

Electrolyte Design for Low‑Temperature Li‑Metal Batteries:Challenges and Prospects

Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation.To get the most energy storage out of the battery at low temperatures,improvements in electrolyte chemistry need to be coupled with optimized electrode materials and tailored electrolyte/electrode interphases.Herein,this review critically outlines electrolytes’limiting factors,including reduced ionic conductivity,large de-solvation energy,sluggish charge transfer,and slow Li-ion transportation across the electrolyte/electrode interphases,which affect the low-temperature performance of Li-metal batteries.Detailed theoretical derivations that explain the explicit influence of temperature on battery performance are presented to deepen understanding.Emerging improvement strategies from the aspects of electrolyte design and electrolyte/electrode interphase engineering are summarized and rigorously compared.Perspectives on future research are proposed to guide the ongoing exploration for better low-temperature Li-metal batteries.

Estimating shear strength of high-level pillars supported with cemented backfilling using the HoekeBrown strength criterion

Deep metal mines are often mined using the high-level pillars with subsequent cementation backfilling(HLSCB)mining method.At the design stage,it is therefore important to have a reasonable method for determining the shear strength of the high-level pillars(i.e.cohesion and internal friction angle)when they are supported by cemented backfilling.In this study,a formula was derived for the upper limit of the confining pressure σ3max on a high-level pillar supported by cemented backfilling in a deep metal mine.A new method of estimating the shear strength of such pillars was then proposed based on the Hoek eBrown failure criterion.Our analysis indicates that the horizontal stress σhh acting on the cemented backfill pillar can be simplified by expressing it as a constant value.A reasonable and effective value for σ3max can then be determined.The value of s3max predicted using the proposed method is generally less than 3 MPa.Within this range,the shear strength of the high-level pillar is accurately calculated using the equivalent MohreCoulomb theory.The proposed method can effectively avoid the calculation of inaccurate shear strength values for the high-level pillars when the original HoekeBrown criterion is used in the presence of large confining pressures,i.e.the situation in which the cohesion value is too large and the friction angle is too small can effectively be avoided.The proposed method is applied to a deep metal mine in China that is being excavated using the HLSCB method.The shear strength parameters of the high-level pillars obtained using the proposed method were input in the numerical simulations.The numerical results show that the recommended level heights and sizes of the high-level pillars and rooms in the mine are rational.

Lithium-Ion Charged Polymer Channels Flattening Lithium Metal Anode

The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.

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.

Flexible, Transparent and Conductive Metal Mesh Films with Ultra‑High FoM for Stretchable Heating and Electromagnetic Interference Shielding

Despite the growing demand for transparent conductive films in smart and wearable electronics for electromagnetic interference(EMI)shielding,achieving a flexible EMI shielding film,while maintaining a high transmittance remains a significant challenge.Herein,a flexible,transparent,and conductive copper(Cu)metal mesh film for EMI shielding is fabricated by self-forming crackle template method and electroplating technique.The Cu mesh film shows an ultra-low sheet resistance(0.18Ω□^(-1)),high transmittance(85.8%@550 nm),and ultra-high figure of merit(>13,000).It also has satisfactory stretchability and mechanical stability,with a resistance increases of only 1.3%after 1,000 bending cycles.As a stretchable heater(ε>30%),the saturation temperature of the film can reach over 110°C within 60 s at 1.00 V applied voltage.Moreover,the metal mesh film exhibits outstanding average EMI shielding effectiveness of 40.4 dB in the X-band at the thickness of 2.5μm.As a demonstration,it is used as a transparent window for shielding the wireless communication electromagnetic waves.Therefore,the flexible and transparent conductive Cu mesh film proposed in this work provides a promising candidate for the next-generation EMI shielding applications.

Correlation between Combined Urinary Metal Exposure and Grip Strength under Three Statistical Models:A Cross-sectional Study in Rural Guangxi

Objective This study aimed to investigate the potential relationship between urinary metals copper(Cu),arsenic(As),strontium(Sr),barium(Ba),iron(Fe),lead(Pb)and manganese(Mn)and grip strength.Methods We used linear regression models,quantile g-computation and Bayesian kernel machine regression(BKMR)to assess the relationship between metals and grip strength.Results In the multimetal linear regression,Cu(β=−2.119),As(β=−1.318),Sr(β=−2.480),Ba(β=0.781),Fe(β=1.130)and Mn(β=−0.404)were significantly correlated with grip strength(P<0.05).The results of the quantile g-computation showed that the risk of occurrence of grip strength reduction was−1.007(95%confidence interval:−1.362,−0.652;P<0.001)when each quartile of the mixture of the seven metals was increased.Bayesian kernel function regression model analysis showed that mixtures of the seven metals had a negative overall effect on grip strength,with Cu,As and Sr being negatively associated with grip strength levels.In the total population,potential interactions were observed between As and Mn and between Cu and Mn(P_(interactions) of 0.003 and 0.018,respectively).Conclusion In summary,this study suggests that combined exposure to metal mixtures is negatively associated with grip strength.Cu,Sr and As were negatively correlated with grip strength levels,and there were potential interactions between As and Mn and between Cu and Mn.

Bifunctional TiO_(2-x)nanofibers enhanced gel polymer electrolyte for high performance lithium metal batteries

Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.

Corrosion behavior of pure metals(Ni and Ti)and alloys(316H SS and GH3535)in liquid GaInSn

In this study,the interactions between a Ga-based liquid metal,GaInSn,and several metal materials,including pure metals(Ni and Ti)and alloys(316H stainless steel(SS)and GH3535),at 650℃were investigated.The aim was to evaluate the corrosion performance and select a suitable candidate material for use as a molten salt manometer diaphragm in thermal energy storage systems.The results indicated that the alloys(316H SS and GH3535)exhibited less corrosion than pure metals(Ni and Ti)in liquid GaInSn.Ga-rich binary intermetallic compounds were found to form on the surfaces of all the tested metal materials exposed to liquid GaInSn,as a result of the decomposition of liquid GaInSn and its reaction with the constituent elements of the metal materials.The corrosion mechanism for all the tested materials exposed to liquid GaInSn was also investigated and proposed,which may aid in selecting the optimal candidate material when liquid GaInSn is used as the pressure-sensing medium.

From VIB‑to VB‑Group Transition Metal Disulfides:Structure Engineering Modulation for Superior Electromagnetic Wave Absorption

The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various fields,such as catalysis,energy storage,sensing,etc.In recent years,a lot of research work on TMDs based functional materials in the fields of electromagnetic wave absorption(EMA)has been carried out.Therefore,it is of great significance to elaborate the influence of TMDs on EMA in time to speed up the application.In this review,recent advances in the development of electromagnetic wave(EMW)absorbers based on TMDs,ranging from the VIB group to the VB group are summarized.Their compositions,microstructures,electronic properties,and synthesis methods are presented in detail.Particularly,the modulation of structure engineering from the aspects of heterostructures,defects,morphologies and phases are systematically summarized,focusing on optimizing impedance matching and increasing dielectric and magnetic losses in the EMA materials with tunable EMW absorption performance.Milestones as well as the challenges are also identified to guide the design of new TMDs based dielectric EMA materials with high performance.

Stability analysis of longwall top-coal caving face in extra-thick coal seams based on an innovative numerical hydraulic support model

The relationship between support and surrounding rock is of great significance to the control of surrounding rock in mining process.In view of the fact that most of the existing numerical simulation methods construct virtual elements and stress servo control to approximately replace the hydraulic support problem,this paper establishes a new numerical model of hydraulic support with the same working characteristics as the actual hydraulic support by integrating numerical simulation software Rhino,Griddle and FLAC3D,which can realize the simulation of different working conditions.Based on this model,the influence mechanism of the supporting strength of hydraulic support on surrounding rock stress regulation and coal stability in front of the top coal caving face in extra thick coal seam were researched.Firstly,under different support intensity,the abutment pressure of the bearing coal and the coal in front of it presents the “three-stage”evolution characteristics.The influence range of support intensity is 15%–30%.Secondly,1.5 MPa is the upper limit of impact that the support strength can have on the front coal failure area.Thirdly,within a displacement range of 2.76 m from the coal wall,a support strength of1.5 MPa provides optimal control of the horizontal displacement of the coal.

Endoscopic-ultrasound-guided biliary drainage with placement of electrocautery-enhanced lumen-apposing metal stent for palliation of malignant biliary obstruction:Updated meta-analysis

BACKGROUND Endoscopic ultrasound-guided biliary drainage using electrocautery-enhanced(ECE)delivery of lumen-apposing metal stent(LAMS)is gradually being re-cognized as a viable palliative technique for malignant biliary obstruction after endoscopic retrograde cholangiopancreatography(ERCP)failure.However,most of the studies that have assessed its efficacy and safety were small and hetero-geneous.Prior meta-analyses of six or fewer studies that were published 2 years ago were therefore underpowered to yield convincing evidence.AIM To update the efficacy and safety of ECE-LAMS for treatment of biliary ob-struction after ERCP failure.METHODS We searched PubMed,EMBASE,and Scopus databases from the inception of the ECE technique to May 13,2022.Primary outcome measure was pooled technical success rate,and secondary outcomes were pooled rates of clinical success,re-intervention,and adverse events.Meta-analysis was performed using a random-effects model following Freeman-Tukey double-arcsine transformation in R soft-ware(version 4.1.3).RESULTS Fourteen eligible studies involving 620 participants were ultimately included.The pooled rate of technical success was 96.7%,and clinical success was 91.0%.Adverse events were reported in 17.5%of patients.Overall reinter-vention rate was 7.3%.Subgroup analyses showed results were generally consistent.CONCLUSION ECE-LAMS has favorable success with acceptable adverse events in relieving biliary obstruction when ERCP is impossible.The consistency of results across most subgroups suggested that this is a generalizable approach.

Analysis of the interaction between bolt-reinforced rock and surface support in tunnels based on convergence-confinement method

To investigate the interaction of the bolt-reinforced rock and the surface support,an analytical model of the convergence-confinement type is proposed,considering the sequential installation of the fully grouted rockbolts and the surface support.The rock mass is assumed to be elastic-brittle-plastic material,obeying the linear Mohr-Coulomb criterion or the non-linear Hoek-Brown criterion.According to the strain states of the tunnel wall at bolt and surface support installation and the relative magnitude between the bolt length and the plastic depth during the whole process,six cases are categorized upon solving the problem.Each case is divided into three stages due to the different effects of the active rockbolts and the passive surface support.The fictitious pressure is introduced to quantify the threedimensional(3D)effect of the tunnel face,and thus,the actual physical location along the tunnel axis of the analytical section can be considered.By using the bolt-rock strain compatibility and the rocksurface support displacement compatibility conditions,the solutions of longitudinal tunnel displacement and the reaction pressure of surface support along the tunnel axis are obtained.The proposed analytical solutions are validated by a series of 3D numerical simulations.Extensive parametric studies are conducted to examine the effect of the typical parameters of rockbolts and surface support on the tunnel displacement and the reaction pressure of the surface support under different rock conditions.The results show that the rockbolts are more effective in controlling the tunnel displacement than the surface support,which should be installed as soon as possible with a suitable length.For tunnels excavated in weak rocks or with restricted displacement control requirements,the surface support should also be installed or closed timely with a certain stiffness.The proposed method provides a convenient alternative approach for the optimization of rockbolts and surface support at the preliminary stage of tunnel design.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.