MnO_(2)has emerged as one of the favored cathode materials for aqueous zinc ion batteries(AZIBs)due to its high theoretical capacity and abundant crystalline structures.However,MnO_(2)cathode generally suffers from po...MnO_(2)has emerged as one of the favored cathode materials for aqueous zinc ion batteries(AZIBs)due to its high theoretical capacity and abundant crystalline structures.However,MnO_(2)cathode generally suffers from poor electrical conductivity and rapid capacity degradation due to unavoidable manganese dissolution during cycling,limiting their further utilization.In this study,we modify the d-band center of Mn by introducing non-precious metal Bi atoms into the MnO_(2)system,thereby strengthening the Mn-O bonding to inhibit manganese dissolution.Theoretical calculations reveal that the d-band center of Mn in Bi-MnO_(2)shifts upward,promoting electron transfer from O 2p orbitals to Mn-O bonding orbitals.This enhances the Mn-O bond strength,stabilizing Mn atoms in the crystal lattice and reducing manganese solvation loss.As a result,the conductivity and cyclic stability of Bi-MnO_(2)are significantly improved.The results demonstrate that Bi-MnO_(2)exhibits outstanding electrochemical properties,with a capacity of 392.3 mAh g^(-1)after 100 cycles at 0.2 A g^(-1)and a capacity retention of 83.25%after 5000 cycles at 1.0 A g^(-1).This study presents a new approach to address the manganese dissolution issue,which could further advance the application of d-band center theory in MnO_(2)materials.展开更多
Due to their high mechanical compliance and excellent biocompatibility,conductive hydrogels exhibit significant potential for applications in flexible electronics.However,as the demand for high sensitivity,superior me...Due to their high mechanical compliance and excellent biocompatibility,conductive hydrogels exhibit significant potential for applications in flexible electronics.However,as the demand for high sensitivity,superior mechanical properties,and strong adhesion performance continues to grow,many conventional fabrication methods remain complex and costly.Herein,we propose a simple and efficient strategy to construct an entangled network hydrogel through a liquid-metal-induced cross-linking reaction,hydrogel demonstrates outstanding properties,including exceptional stretchability(1643%),high tensile strength(366.54 kPa),toughness(350.2 kJ m^(−3)),and relatively low mechanical hysteresis.The hydrogel exhibits long-term stable reusable adhesion(104 kPa),enabling conformal and stable adhesion to human skin.This capability allows it to effectively capture high-quality epidermal electrophysiological signals with high signal-to-noise ratio(25.2 dB)and low impedance(310 ohms).Furthermore,by integrating advanced machine learning algorithms,achieving an attention classification accuracy of 91.38%,which will significantly impact fields like education,healthcare,and artificial intelligence.展开更多
Here we fabricate LA103Z Mg-Li alloy via wire-arc directed energy deposition(WA-DED),and subsequent aging treatment is employed to improve its mechanical property.Results show that a typical dual-phase microstructure ...Here we fabricate LA103Z Mg-Li alloy via wire-arc directed energy deposition(WA-DED),and subsequent aging treatment is employed to improve its mechanical property.Results show that a typical dual-phase microstructure is formed upon WA-DED,consisting of α-Mg,β-Li,AlLi and Li_(2)MgAl,with negligible porosity,and the core-shell Li_(2)MgAl/AlLi composite particles are also generated.After aging treatment,the microstructure is slightly coarsened,together with the precipitation of nano-sized D0_(3)-Mg_(3)Al particles,as well as the dissolution and the mergence of α-Mg phases.Negligible strength and ductility anisotropies are found for the as-deposited alloy.Significant strength increment is achieved via aging treatment,and the ultimate strength increases by~20%(~34 MPa),reaching 200±1 MPa.Both as-deposited and aged alloys show acceptable uniform elongation,with a transgranular fracture mode.Precipitation strengthening enabled by nano-sized D0_(3)-Mg_(3)Al precipitates is primarily responsible for the strength increment mediated by aging treatment.Grain refinement strengthening and solid solution strengthening provide additional contributions to the improved strength.Our work thus offers an applicable additive manufacturing pathway for the efficient and safety-guaranteed fabrication of Mg-Li alloy components with decent mechanical property.展开更多
MXene,with metallic conductivity,strong hydrophilicity,and rich chemistries,has been widely used as electrode material for energy storage.However,the notorious issues of aggregation and oxidation for MXene significant...MXene,with metallic conductivity,strong hydrophilicity,and rich chemistries,has been widely used as electrode material for energy storage.However,the notorious issues of aggregation and oxidation for MXene significantly inhibit its electrochemical performance and further wide application.Herein,a physicochemical double protection strategy is proposed to stabilize MXene in the hydrothermal process effectively.Polyvinylpyrrolidone(PVP),with the structure of a long chain and abundant O/N function groups,provides physical protection against agglomeration(steric effect)and chemical protection against oxidation(electron transfer)at the same time,contributing to the synthesis of MXene-based hybrids with high conductivity and fully exposed active sites.As proof of the concept,2D MXene/Co_(9)S_(8) nanohybrids with a scaly surface are fabricated and present impressive performance,especially rate performance for hybrid supercapacitor(HSC)with MoS_(2) as the counter electrode.The HSC demonstrates a high energy density of 111 Wh kg^(-1) at 845 W kg^(-1) and an excellent rate performance of 61 Wh kg^(-1) at 16.9 kW kg^(-1).展开更多
Nickel(II)as one of the primary categories of heavy metals can lead to serious health problems if achieving the critical levels in the water.Thus,it is vital to propose a stable,reliable,and economical approach for de...Nickel(II)as one of the primary categories of heavy metals can lead to serious health problems if achieving the critical levels in the water.Thus,it is vital to propose a stable,reliable,and economical approach for detecting Ni ions.The microfluidic paper-based analytical devices(µPADs)are potential candidates for the detection of water quality parameters including pH,heavy ions,nitrite and so on.However,it suffers from a huge error caused by the environment and artificial mistakes.In this study,we proposed an improved technique route to increase the stability and reliability of microfluidic paper-based analytical devices.The main technique points include a stable light source,a matched camera,improved reliability of the devices,and effective calculated methods.Finally,we established 15 standard curves that could be used to detect nickel ions and obtained uniform colorimetric results with reliability and repeatability.With those improvements,the relative errors for the five types of real water samples from the Zhongshan industrial parks were reduced to 0.26%,14.78%,24.20%,50.29%and 3.53%,respectively.These results were conducive to exploring this technique for the detection of nickel ions in wastewater from the Zhongshan industrial parks.The results demonstrated that the above technique route is promising for the detection of other heavy metal ions in industrial effluent.展开更多
Excellent heat affected zone(HAZ)toughness technology improved by strong deoxidizers(ETISI)technology has been developed by Baosteel.In the deoxidation process of molten steel by adding strong deoxidizers,the formatio...Excellent heat affected zone(HAZ)toughness technology improved by strong deoxidizers(ETISI)technology has been developed by Baosteel.In the deoxidation process of molten steel by adding strong deoxidizers,the formation of micrometer inclusions and nano-meter precipitates in steel plates can be effectively controlled by a precise control of oxygen concentration.In the welding process with a high-heat input,the formation of acicular ferrite can be selectively promoted with the aid of the micrometer inclusions;the growth ofγgrains can also be selectively restrained by the pinning effect of the nano-meter precipitates.After welding with a high-heat input of 400 kJ/cm,excellent HAZ toughness can be obtained in the steel plates with both of the above microstructures,and the average absorbed energy is greater than 200 J for the V-notch Charpy impact test at-20℃.展开更多
Seeking for extremely active and durable bifunctional electrocatalysts towards the overall water splitting possesses a strategic significance on the development of sustainable and clean energy for the replacement of f...Seeking for extremely active and durable bifunctional electrocatalysts towards the overall water splitting possesses a strategic significance on the development of sustainable and clean energy for the replacement of fossil fuels.Ir-based nanomaterials are deemed as one of the most highefficiency oxygen evolution reaction electrocatalysts while the hydrogen evolution reaction performance is unfavorable.In this work,we report a one-pot hydrothermal synthesis of N-doped graphene anchored Ir nanoparticles(Ir/N-rGO) with ultrasmall particle size(~2.0 nm).Apart from the predictably superior OER performance,the resultant Ir/N-rGO also displays excellent hydrogen evolution reaction(HER) performance,requiring merely 76 and 260 mV overpotentials to achieve the current density of 10 mA cm^(-2) towards HER and OER,respectively.When applied as the bifunctional electrodes for overall water splitting,Ir/N-rGO needs a lower overpotential(1.74 V) to achieve a current density of50 mA cm^(-2) in alkaline solution,exceeding that of Pt/C and RuO_(2) couple(1.85 V).Thus,the as-fabricated Ir/N-rGO has a commendable prospect in the practical application of alkaline water electrocatalysis.展开更多
The development of potential transition-metal carbide/nitride heterojunctions is hindered by overall understanding and precise modulation for heterointerface effects.Herein,we demonstrate that Mo_(2)C/Mo_(2)N heteroju...The development of potential transition-metal carbide/nitride heterojunctions is hindered by overall understanding and precise modulation for heterointerface effects.Herein,we demonstrate that Mo_(2)C/Mo_(2)N heterojunction with the precisely regulated high-quality interface can achieve marvelous rate performance and energy output via enlarging the interface-effect range and maximizing "accelerated charge" amount The heterointerface mechanism improving properties is synergistically revealed from kinetics and thermodynamics perspectives.Kinetics analysis confirms that the self-built electric field affords a robust force to drive rapid interface electrons/ions migration.The small adsorption energy,high density of states and quite low diffusion barrier thermodynamically enhance the electrochemical reaction dynamics on heterointerface.Consequently,the almost optimal performance of ultrahigh capacitance retention(85.6% even at 10 A g^(-1)) and pronounced energy output(96.4 Wh kg^(-1))in hybridsupercapacitors than other Mo_(2)C/Mo_(2)N-based materials is presented.This work gives new insight into the energy storage mechanism of heterojunction and guides the design of advanced electrodes.展开更多
The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herei...The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herein,we proposed an Al and O dual-doped strategy for Li_(3)PS_(4)SE to regulate the chemical/electrochemical stability of anionic PS_(4)^(3-)tetrahedra to mitigate structural hydrolysis and parasitic reactions at the SE/Li interface.The optimized Li_(3.08)A_(10.04)P_(0.96)S_(3.92)O_(0.08)SE presents the highestσLi+of 3.27 mS cm^(-1),which is~6.8 times higher than the pristine Li_(3)PS_(4)and excellently inhibits the structural hydrolysis for~25 min@25%humidity at RT.DFT calculations confirmed that the enhanced chemical stability was revealed to the intrinsically stable entities,e.g.,POS33-units.Moreover,Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE cycled stably in Li//Li symmetric cell over 1000 h@0.1 mA cm^(-2)/0.1 mA h cm^(-2),could be revealed to Li-Al alloy and Li_(2)Oat SE/Li interface impeding the growth of Li-dendrites during cycling.Resultantly,LNO@LCO/Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)/Li-In cell delivered initial discharge capacities of 129.8 mA h g^(-1)and 83.74%capacity retention over 300 cycles@0.2 C at RT.Moreover,the Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE presented>90%capacity retention over 200 and 300 cycles when the cell was tested with LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)cathode material vs.5 and 10 mg cm^(-2)@RT.展开更多
Considering the importance and complexity of benzene oxidation on mineral oxide aerosol surfaces in the atmosphere,gas-phase 3 d-transition metal oxide cations were used as models of active sites on mineral oxide aero...Considering the importance and complexity of benzene oxidation on mineral oxide aerosol surfaces in the atmosphere,gas-phase 3 d-transition metal oxide cations were used as models of active sites on mineral oxide aerosols to mimic the corresponding reactions.The various cations have been prepared by laser ablation and reacted with benzene in a linear ion trap reactor.Of the 103 systematically investigated cations,39 clusters can oxidize benzene at room temperature.In addition to the adsorption channel,other five types of reaction channels were observed,including dehydrogenation of C6H6,charge exchange,hydrogen atom transfer,oxygen atom transfer,and the formation of C6H5O^+radical,among which the first two pathways are prevale nt and the formation of C6H6O^+cations has not been reported in literature.The insight into the benzene oxidation reactions derived from the gas-phase model systems is helpful to build a detailed picture of oxidative mechanisms of C6H6 and its derivatives over corresponding mineral oxide aerosols.展开更多
Photoacoustic imaging(PAI)is a new biomedical imaging technology that provides a mixed contrast mechanism and excellent spatial resolution in biological tissues.It is a non-invasive technology that can provide in vivo...Photoacoustic imaging(PAI)is a new biomedical imaging technology that provides a mixed contrast mechanism and excellent spatial resolution in biological tissues.It is a non-invasive technology that can provide in vivo anatomical and functional information.This technology has great application potential in microscopic imaging and endoscope system.In recent years,the devel-opment of micro electro mechanical system(MEMS)technology has promoted the improvement and miniaturization of the photoacoustic imaging system,as well as its preclinical and clinical appli-cations.This paper introduces the research progress of MEMS technology in photoacoustic micro-scope systems and the miniaturization of photoacoustic endoscope ultrasonic transducers,and points out the shortcomings of existing technology and the direction of future development.展开更多
The space-confined synthesis method has been an efficient way for the preparation of linear carbon chains.However,the large-scale preparation of linear carbon chains still faces many challenges due to the lack of meth...The space-confined synthesis method has been an efficient way for the preparation of linear carbon chains.However,the large-scale preparation of linear carbon chains still faces many challenges due to the lack of methods for the large-scale synthesis of precursors,such as short carbon chains(polyynes),and regulation technology for the transport of reactants in one-dimensional space.Here,we report a facile method for the rapid preparation of polyynes in large quantities using a commercial laser marking machine.Spectroscopic characterizations show that a large number of polyynes,such as C_(8)H_(2),C_(10)H_(2),C_(12)H_(2),and C_(14)H_(2),can be produced by ablating the graphite plate immersed in the organic liquid using a laser marking machine.The results of in situ Raman spectroscopy investigation of C_(2n)H_(2)-filled single-walled carbon nanotubes further confirm that a variety of polyyne molecules are synthesized.Meanwhile,in situ Raman spectroscopy also shows that the local heating treatment can accelerate the filling process of C_(2n)H_(2)into one-dimensional channels.This work provides new insights into the study of linear carbon chains and space-confined synthesis methods.展开更多
In this study,Cicada chrysalis protein(CCP)was enzymatically hydrolyzed using alkaline protease 6L,followed by ultrafiltration and preparative high-performance liquid chromatography(prep-HPLC)for fractionation.The opt...In this study,Cicada chrysalis protein(CCP)was enzymatically hydrolyzed using alkaline protease 6L,followed by ultrafiltration and preparative high-performance liquid chromatography(prep-HPLC)for fractionation.The optimal peptide fractions were identified through nano-HPLC-MS/MS,leading to the discovery of four novel angiotensin-converting enzyme(ACE)inhibitory peptides:FRGF,SPRPW,GPKLF,and SYRF.The IC50 values for these peptides were determined to be 1.716 mg/mL,0.34 mg/mL,0.118 mg/mL,and 0.026 mg/mL,respectively.Molecular interaction analysis revealed that these peptides primarily bind to key residues within the ACE active site via hydrogen bonding.Isothermal titration calorimetry(ITC)further confirmed the binding of all peptides to the ACE active site,revealing a compensatory relationship between entropy and enthalpy during the binding process.Notably,GPKLF and SYRF were shown to significantly increase nitric oxide(NO)production in human umbilical vein endothelial cells(HUVECs)while reducing endothelin-1(ET-1)secretion.By inhibiting the ACE/AT1R axis and ET-1 expression,while simultaneously activating the ACE2/Ang1-7 axis and NO signaling pathway,these bioactive peptides help restore the balance of the renin-angiotensin system and enhance endothelial function,thereby exerting their protective effects on cardiovascular health.The results of this study suggest that CPP may serve as a promising source of ACE inhibitory peptides,offering a theoretical foundation for the development of functional foods with antihypertensive properties.展开更多
The speciation of Se varies among different plants.Predominant Se species in the protein digestion products of Cardamine violifolia(H-CVP),soybean(H-SBP),and cabbage(H-CBP)are SeCys_(2),SeMet,and Se(VI),respec-tively....The speciation of Se varies among different plants.Predominant Se species in the protein digestion products of Cardamine violifolia(H-CVP),soybean(H-SBP),and cabbage(H-CBP)are SeCys_(2),SeMet,and Se(VI),respec-tively.This study aims to elucidate the neuroprotective effects,bioavailability and transport mechanism of Se in Se-enriched proteins with different Se species.Compared to low-Se protein digestion products,Se-enriched protein digestion products significantly reduced Aβ_(1-42) induced apoptosis in PC-12 cells at the same protein matrix,especially H-CVP(increased by 32.4%relative to the control group).These results indicated that Se enrichment significantly enhances the neuroprotective effects of plant-derived proteins.In addition,H-SBP exerted neuroprotective effects by reducing caspase-9 activity by 42%,whereas H-CVP significantly decreased caspase-3 activity by 29%.The bioavailability of total Se in H-CVP,H-SBP and H-CBP were 29.07%,44.90%and 26.11%,respectively.Se species might also influence the bioavailability of Se,thereby affecting its neuro-protective activity.Furthermore,the transport of the three Se-enriched proteins was energy-dependent and some active transport carriers may be involved in their transmembrane transport.The novel organic cation and plasma membrane monoamine transporter families were participated the absorption of Se while multidrug resistance related protein families regulated the effluxion of Se in H-SBP and H-CVP group.For the H-CBP,organic anion transporters and P-protein families influenced the absorption and effluxion of Se.This study provides a basis for further studies on the roles of different Se species in the neuroprotective effects and bioavailability of Se-enriched proteins.展开更多
Epigallocatechin-3-gallate(EGCG)is a natural polyphenol with potent antioxidant and anticancer activities;however,its biomedical application is hindered by poor stability and high susceptibility to environmental degra...Epigallocatechin-3-gallate(EGCG)is a natural polyphenol with potent antioxidant and anticancer activities;however,its biomedical application is hindered by poor stability and high susceptibility to environmental degradation.In this study,we employed Mannich condensation reaction between EGCG and selenocystine(SeCys_(2))to construct EGCG-based nanoparticles(ESNPs)in aqueous media for tumor inhibition.FTIR,^(1)H NMR,and STEM analyses verified that ESNPs possessed a robust cross-linked three-dimensional network architecture,characterized by C-O-C,C-N-C,and C-Se-C bonds.The resulting ESNPs exhibited uniform spherical morphology,improved colloidal stability,and homogeneous selenium(Se)distribution.Cellular assays revealed that ESNPs were efficiently internalized by Hepa1-6 and SCC-7 cells and predominantly accumulated in the perinuclear region,where they induced pronounced oxidative stress,lipid peroxidation,DNA damage,and subsequent apoptosis.ESNPs displayed substantially enhanced anti-tumor activity against PC12,Hepa1-6,SCC-7,and LLC cells,yielding IC_(50)values of 24.77,18.71,34.04,and 34.96μg/mL,respectively,significantly lower than those of free EGCG,SeCys2,or their physical mixture.Notably,ESNPs exhibited reduced toxicity toward normal C2C12 cells,demonstrating favorable tumor selectivity.Overall,this work presents a simple and green strategy for the construction of natural polyphenol-Se hybrid nanoparticles with synergistic redox regulation and apoptosis-inducing capabilities.展开更多
Garnet-type ceramic Li-La_(3)Zr_(2)O_(12)(LLZO)stands out as a potential solid-state electrolyte,offering a promising alternative to conventional flammable liquid electrolytes.However,its large interfacial resistance ...Garnet-type ceramic Li-La_(3)Zr_(2)O_(12)(LLZO)stands out as a potential solid-state electrolyte,offering a promising alternative to conventional flammable liquid electrolytes.However,its large interfacial resistance with electrodes remains a significant challenge.In this research,we have successfully in-situ fabricated polymeric interface layers on both cathode and anode sides with LLZO.By tuning the gel-polymer interphase via fluoroethylene carbonate(FEC),known as FGPE,we have established a rapid Li^(+) transport channel by enhancing the solid-solid interfacial contact.This FGPE layer exhibits exceptional ionic conductivity of 1.38 mS/cm and a high Li-ion transference number of 0.64.Furthermore,FGPE effectively mitigates concentration polarization under high currents,thereby enabling a higher capacity output.In comparison to gel-polymer interphases with dimethyl carbonate(DMC)as the solvent(referred to as GPE),the Li|FGPE|Li symmetrical cell has demonstrated superior stability in plating/strapping performance over800h at a current density of 0.1 mA/cm^(2).Moreover,the Li|FGPE|LLZO|FGPE|LiFePO_(4) cell has exhibited commendable rate capability and has maintained a high capacity retention of 98.94%at 0.5 C after 200cycles.This study underscores an innovative approach in advancing in field of solid-state batteries,anticipated to be broadly applicable to other solid-state batteries by facilitating an abundance of robust solid-solid interfacial contacts.展开更多
Electrocatalytic ammonia oxidation reaction(AOR)represents a sustainable synthesis approach for valuable nitrogen‑containing compounds like nitrites and nitrates.However,the numerous AOR intermediates often complicate...Electrocatalytic ammonia oxidation reaction(AOR)represents a sustainable synthesis approach for valuable nitrogen‑containing compounds like nitrites and nitrates.However,the numerous AOR intermediates often complicate the precise regulation of target intermediate adsorption,hindering the efficient and selective nitrate/nitrite production.We herein present a NiCu‑BDC MOF with tunable AOR product selectivity,which undergoes a controllable in situ reconstruction into Cu‑β‑NiOOH at 1.7 V vs.RHE,enabling the shift of the reaction pathway from NH_(4)^(+)‑to‑NO_(2)^(−)to NH_(4)^(+)‑to‑NO_(3)^(−).The unique restructuring behavior of this material,combined with its dense active sites,enables highly selective production of nitrites and nitrates(94.9%NO_(2)^(−)selectivity at 1.60 V vs.RHE and 92.6%NO_(3)^(−)selectivity at 1.95 V vs.RHE).Theoretical simulations reveal that the Cu incorporation in NiCu‑BDC modulates the electronic configuration of Ni sites,facilitating moderate adsorption of key NO and NOOH intermediates,thus promoting efficient nitrite generation at low potentials.At higher potentials,NiCu‑BDC undergoes reconstruction to Cu‑β‑NiOOH,stabilizing the conversion of NO_(2)to NO_(2)OH,making nitrate formation thermodynamically favorable and a rapid selectivity shift.This potential‑driven selectivity control not only provides a new strategy for efficient nitrites/nitrates synthesis by simply adjusting applied potentials but also provides fundamental insights into regulating selectivity in multi‑product electrochemical reactions.展开更多
The electrochemical conversion of CO_(2) into value-added chemicals presents an environmentally sustainable alternative to conventional fossil-derived processes,yet achieving high selectivity remains challenging due t...The electrochemical conversion of CO_(2) into value-added chemicals presents an environmentally sustainable alternative to conventional fossil-derived processes,yet achieving high selectivity remains challenging due to competing reaction pathways.Here,we demonstrate precise tuning of CO_(2) electroreduction pathways through femtosecond laser-driven surface doping of Cu with targeted metals,achieving Faradaic efficiencies of 58.9%for CO,67.9%for formate,and 37.8%for ethylene.This spatially shaping laser technique enables nanoscale deposition of any metal(including Sb,Sn,Re,La,In,Co,Ni,Ag,and Pt)onto Cu foil,forming compositionally graded Cu-based bimetallic surfaces with controlled atomic ratios.Systematic electronic structure analysis reveals that secondary metals induce d-band center shifts spanning−0.21 to+0.78 eV,governing intermediate adsorption energetics-upward shifts strengthen*CO binding via enhanced back-donation,while downward shifts generally weaken adsorbate interactions.Through precise control of Cu/Sn and Cu/Sb atomic ratios,we manipulate electronic structures of CuSn and CuSb catalysts and consequently demonstrate continuous tuning of formate(19.0%-67.9%)and CO(18.8%-58.9%)selectivity.In-situ Raman spectroscopy and valence band X-ray photoelectron spectroscopy(XPS)elucidate dual modulation mechanisms.Sn enhances CO desorption by weakening*CO adsorption,whereas La promotes ethylene formation through optimized CO absorption and dimerization.The tunability of the reaction pathways aligns with metal-dependent stabilization of critical intermediates(CO and*OCHO).This work introduces a nanoscale-depth and trace-level multi-elemental loading strategy with tunable ratios on copper electrodes,enabling precise electronic structure manipulation of Cu-based electrocatalysts to mechanistically elucidate the correlation between surface electronic states and product selectivity,offering a roadmap to design and modulate Cu-based catalysts for selective CO_(2)-to-chemical conversion and beyond via low-cost laser processing techniques.展开更多
Elucidation of a physicochemical process on nanocatalysts,especially under continuously evolving conditions,is often heavily tool-driven because of technical challenges.Recently,ambient pressure X-ray photoelectron sp...Elucidation of a physicochemical process on nanocatalysts,especially under continuously evolving conditions,is often heavily tool-driven because of technical challenges.Recently,ambient pressure X-ray photoelectron spectroscopy(APXPS)emerges as an emerging photon-in-electron-out technique in in-situ/operando analysis by bridging the pressure-gap between conventional ultra-high vacuum(UHV)and near ambient or even close to operating conditions,rendering the advancement of XPS from a UHV-based technique to a versatile and powerful tool that enables the specific probe of numerous events taking place at the gas–solid,liquid–solid and liquid–gas nanoscale interfaces which are critical to nanocatalysis research.For example,APXPS probes information on catalytically active phase and reaction kinetics in nanocatalytic processes;details inside the electric double-layer at an electrolyte/electrode interface can now be accessed;more efficient nanocatalyst design can be achieved and energy transfer venues can be optimized.Here,we aim to critically review the recent advances in instrumentation and the probe of the gas–solid,liquid–solid,and gas–liquid nanoscale interfaces using APXPS-based methodologies,followed by putting forward an outlook of development of APXPS as a rising in-situ/operando analytical means in surface science,nanocatalysis,nanoscience materials science.展开更多
Developing facile methods to construct hierarchical-structured transition metal phosphides is beneficial for achieving high-efficiency hydrogen evolution catalysts.Herein,a self-template strategy of hydrothermal treat...Developing facile methods to construct hierarchical-structured transition metal phosphides is beneficial for achieving high-efficiency hydrogen evolution catalysts.Herein,a self-template strategy of hydrothermal treatment of solid Ni-Co glycerate nanospheres followed by phosphorization is delivered to synthesize hierarchical Ni Co P hollow nanoflowers with ultrathin nanosheet assembly.The microstructure of Ni Co P can be availably tailored by adjusting the hydrothermal treatment temperature through affecting the hydrolysis process of Ni-Co glycerate nanospheres and the occurred Kirkendall effect.Benefitting from the promoted exposure of active sites and affluent mass diffusion routes,the HER performance of the Ni Co P hollow nanoflowers has been obviously enhanced in contrast with the solid Ni Co P nanospheres.The fabricated Ni Co P hollow nanoflowers yield the current density of 10 m A cmà2at small overpotentials of 95 and 127 m V in 0.5 mol Là1H2SO4and 1.0 mol Là1KOH solution,respectively.Moreover,the two-electrode alkaline cell assembled with the Ni Co P and Ir/C catalysts exhibits sustainable stability for overall water splitting.The work provides a simple but efficient method to regulate the microstructure of transition metal phosphides,which is helpful for achieving high-performance hydrogen evolution catalysts based on solid-state metal alkoxides.展开更多
基金supported by the Beijing Natural Science Foundation(No.2202050).
文摘MnO_(2)has emerged as one of the favored cathode materials for aqueous zinc ion batteries(AZIBs)due to its high theoretical capacity and abundant crystalline structures.However,MnO_(2)cathode generally suffers from poor electrical conductivity and rapid capacity degradation due to unavoidable manganese dissolution during cycling,limiting their further utilization.In this study,we modify the d-band center of Mn by introducing non-precious metal Bi atoms into the MnO_(2)system,thereby strengthening the Mn-O bonding to inhibit manganese dissolution.Theoretical calculations reveal that the d-band center of Mn in Bi-MnO_(2)shifts upward,promoting electron transfer from O 2p orbitals to Mn-O bonding orbitals.This enhances the Mn-O bond strength,stabilizing Mn atoms in the crystal lattice and reducing manganese solvation loss.As a result,the conductivity and cyclic stability of Bi-MnO_(2)are significantly improved.The results demonstrate that Bi-MnO_(2)exhibits outstanding electrochemical properties,with a capacity of 392.3 mAh g^(-1)after 100 cycles at 0.2 A g^(-1)and a capacity retention of 83.25%after 5000 cycles at 1.0 A g^(-1).This study presents a new approach to address the manganese dissolution issue,which could further advance the application of d-band center theory in MnO_(2)materials.
基金supported by the National Key Research&Development Program of China(grant no.2022YFC3500503)the National Natural Science Foundation of China(grant nos.62227807,12374171,12004034,62402041)+2 种基金the Beijing Institute of Technology Research Fund Program for Young Scholars,Chinathe Fundamental Research Funds for the Central Universities(grant nos.2024CX06060)Beijing Youth Talent Lifting Project.
文摘Due to their high mechanical compliance and excellent biocompatibility,conductive hydrogels exhibit significant potential for applications in flexible electronics.However,as the demand for high sensitivity,superior mechanical properties,and strong adhesion performance continues to grow,many conventional fabrication methods remain complex and costly.Herein,we propose a simple and efficient strategy to construct an entangled network hydrogel through a liquid-metal-induced cross-linking reaction,hydrogel demonstrates outstanding properties,including exceptional stretchability(1643%),high tensile strength(366.54 kPa),toughness(350.2 kJ m^(−3)),and relatively low mechanical hysteresis.The hydrogel exhibits long-term stable reusable adhesion(104 kPa),enabling conformal and stable adhesion to human skin.This capability allows it to effectively capture high-quality epidermal electrophysiological signals with high signal-to-noise ratio(25.2 dB)and low impedance(310 ohms).Furthermore,by integrating advanced machine learning algorithms,achieving an attention classification accuracy of 91.38%,which will significantly impact fields like education,healthcare,and artificial intelligence.
基金supported by the National Natural Science Foundation of China(52475320).
文摘Here we fabricate LA103Z Mg-Li alloy via wire-arc directed energy deposition(WA-DED),and subsequent aging treatment is employed to improve its mechanical property.Results show that a typical dual-phase microstructure is formed upon WA-DED,consisting of α-Mg,β-Li,AlLi and Li_(2)MgAl,with negligible porosity,and the core-shell Li_(2)MgAl/AlLi composite particles are also generated.After aging treatment,the microstructure is slightly coarsened,together with the precipitation of nano-sized D0_(3)-Mg_(3)Al particles,as well as the dissolution and the mergence of α-Mg phases.Negligible strength and ductility anisotropies are found for the as-deposited alloy.Significant strength increment is achieved via aging treatment,and the ultimate strength increases by~20%(~34 MPa),reaching 200±1 MPa.Both as-deposited and aged alloys show acceptable uniform elongation,with a transgranular fracture mode.Precipitation strengthening enabled by nano-sized D0_(3)-Mg_(3)Al precipitates is primarily responsible for the strength increment mediated by aging treatment.Grain refinement strengthening and solid solution strengthening provide additional contributions to the improved strength.Our work thus offers an applicable additive manufacturing pathway for the efficient and safety-guaranteed fabrication of Mg-Li alloy components with decent mechanical property.
基金financially supported by the Beijing Natural Science Founding(No.2202050)the National Natural Science Foundation of China(No.21111120074).
文摘MXene,with metallic conductivity,strong hydrophilicity,and rich chemistries,has been widely used as electrode material for energy storage.However,the notorious issues of aggregation and oxidation for MXene significantly inhibit its electrochemical performance and further wide application.Herein,a physicochemical double protection strategy is proposed to stabilize MXene in the hydrothermal process effectively.Polyvinylpyrrolidone(PVP),with the structure of a long chain and abundant O/N function groups,provides physical protection against agglomeration(steric effect)and chemical protection against oxidation(electron transfer)at the same time,contributing to the synthesis of MXene-based hybrids with high conductivity and fully exposed active sites.As proof of the concept,2D MXene/Co_(9)S_(8) nanohybrids with a scaly surface are fabricated and present impressive performance,especially rate performance for hybrid supercapacitor(HSC)with MoS_(2) as the counter electrode.The HSC demonstrates a high energy density of 111 Wh kg^(-1) at 845 W kg^(-1) and an excellent rate performance of 61 Wh kg^(-1) at 16.9 kW kg^(-1).
基金funded by the Beijing Natural Science Foundation[Grant No.Z210006]the National Natural Science Foundation of China[Grant No.62275061].
文摘Nickel(II)as one of the primary categories of heavy metals can lead to serious health problems if achieving the critical levels in the water.Thus,it is vital to propose a stable,reliable,and economical approach for detecting Ni ions.The microfluidic paper-based analytical devices(µPADs)are potential candidates for the detection of water quality parameters including pH,heavy ions,nitrite and so on.However,it suffers from a huge error caused by the environment and artificial mistakes.In this study,we proposed an improved technique route to increase the stability and reliability of microfluidic paper-based analytical devices.The main technique points include a stable light source,a matched camera,improved reliability of the devices,and effective calculated methods.Finally,we established 15 standard curves that could be used to detect nickel ions and obtained uniform colorimetric results with reliability and repeatability.With those improvements,the relative errors for the five types of real water samples from the Zhongshan industrial parks were reduced to 0.26%,14.78%,24.20%,50.29%and 3.53%,respectively.These results were conducive to exploring this technique for the detection of nickel ions in wastewater from the Zhongshan industrial parks.The results demonstrated that the above technique route is promising for the detection of other heavy metal ions in industrial effluent.
文摘Excellent heat affected zone(HAZ)toughness technology improved by strong deoxidizers(ETISI)technology has been developed by Baosteel.In the deoxidation process of molten steel by adding strong deoxidizers,the formation of micrometer inclusions and nano-meter precipitates in steel plates can be effectively controlled by a precise control of oxygen concentration.In the welding process with a high-heat input,the formation of acicular ferrite can be selectively promoted with the aid of the micrometer inclusions;the growth ofγgrains can also be selectively restrained by the pinning effect of the nano-meter precipitates.After welding with a high-heat input of 400 kJ/cm,excellent HAZ toughness can be obtained in the steel plates with both of the above microstructures,and the average absorbed energy is greater than 200 J for the V-notch Charpy impact test at-20℃.
基金financially supported by the National Natural Science Foundation of China (21875112)the Natural Science Foundation of Jiangsu Province (BK20171473)+1 种基金support from the National and Local Joint Engineering Research Center of Biomedical Functional Materialsa project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘Seeking for extremely active and durable bifunctional electrocatalysts towards the overall water splitting possesses a strategic significance on the development of sustainable and clean energy for the replacement of fossil fuels.Ir-based nanomaterials are deemed as one of the most highefficiency oxygen evolution reaction electrocatalysts while the hydrogen evolution reaction performance is unfavorable.In this work,we report a one-pot hydrothermal synthesis of N-doped graphene anchored Ir nanoparticles(Ir/N-rGO) with ultrasmall particle size(~2.0 nm).Apart from the predictably superior OER performance,the resultant Ir/N-rGO also displays excellent hydrogen evolution reaction(HER) performance,requiring merely 76 and 260 mV overpotentials to achieve the current density of 10 mA cm^(-2) towards HER and OER,respectively.When applied as the bifunctional electrodes for overall water splitting,Ir/N-rGO needs a lower overpotential(1.74 V) to achieve a current density of50 mA cm^(-2) in alkaline solution,exceeding that of Pt/C and RuO_(2) couple(1.85 V).Thus,the as-fabricated Ir/N-rGO has a commendable prospect in the practical application of alkaline water electrocatalysis.
基金supported by the Beijing Natural Science Founding (2202050)the Beijing Institute of Technology scientific cooperation project (BITBLR2020010)+1 种基金the National Nature Science Foundation of China (21111120074)the National Nature Science Foundation of China (20806008)。
文摘The development of potential transition-metal carbide/nitride heterojunctions is hindered by overall understanding and precise modulation for heterointerface effects.Herein,we demonstrate that Mo_(2)C/Mo_(2)N heterojunction with the precisely regulated high-quality interface can achieve marvelous rate performance and energy output via enlarging the interface-effect range and maximizing "accelerated charge" amount The heterointerface mechanism improving properties is synergistically revealed from kinetics and thermodynamics perspectives.Kinetics analysis confirms that the self-built electric field affords a robust force to drive rapid interface electrons/ions migration.The small adsorption energy,high density of states and quite low diffusion barrier thermodynamically enhance the electrochemical reaction dynamics on heterointerface.Consequently,the almost optimal performance of ultrahigh capacitance retention(85.6% even at 10 A g^(-1)) and pronounced energy output(96.4 Wh kg^(-1))in hybridsupercapacitors than other Mo_(2)C/Mo_(2)N-based materials is presented.This work gives new insight into the energy storage mechanism of heterojunction and guides the design of advanced electrodes.
基金supported by the National Natural Science Foundation of China(Nos.21203008,21975025,12274025)the Hainan Province Science and Technology Special Fund(Nos.ZDYF2021SHFZ232,ZDYF2023GXJS022)the Hainan Province Postdoctoral Science Foundation(No.300333)。
文摘The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herein,we proposed an Al and O dual-doped strategy for Li_(3)PS_(4)SE to regulate the chemical/electrochemical stability of anionic PS_(4)^(3-)tetrahedra to mitigate structural hydrolysis and parasitic reactions at the SE/Li interface.The optimized Li_(3.08)A_(10.04)P_(0.96)S_(3.92)O_(0.08)SE presents the highestσLi+of 3.27 mS cm^(-1),which is~6.8 times higher than the pristine Li_(3)PS_(4)and excellently inhibits the structural hydrolysis for~25 min@25%humidity at RT.DFT calculations confirmed that the enhanced chemical stability was revealed to the intrinsically stable entities,e.g.,POS33-units.Moreover,Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE cycled stably in Li//Li symmetric cell over 1000 h@0.1 mA cm^(-2)/0.1 mA h cm^(-2),could be revealed to Li-Al alloy and Li_(2)Oat SE/Li interface impeding the growth of Li-dendrites during cycling.Resultantly,LNO@LCO/Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)/Li-In cell delivered initial discharge capacities of 129.8 mA h g^(-1)and 83.74%capacity retention over 300 cycles@0.2 C at RT.Moreover,the Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE presented>90%capacity retention over 200 and 300 cycles when the cell was tested with LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)cathode material vs.5 and 10 mg cm^(-2)@RT.
基金supported by National Key R&D Program of China(No.2016YFC0203000)the National Natural Science Foundation of China(No.21503015)the Fundamental Research Funds for the Central Universities(Nos.22050205,2017CX01008)。
文摘Considering the importance and complexity of benzene oxidation on mineral oxide aerosol surfaces in the atmosphere,gas-phase 3 d-transition metal oxide cations were used as models of active sites on mineral oxide aerosols to mimic the corresponding reactions.The various cations have been prepared by laser ablation and reacted with benzene in a linear ion trap reactor.Of the 103 systematically investigated cations,39 clusters can oxidize benzene at room temperature.In addition to the adsorption channel,other five types of reaction channels were observed,including dehydrogenation of C6H6,charge exchange,hydrogen atom transfer,oxygen atom transfer,and the formation of C6H5O^+radical,among which the first two pathways are prevale nt and the formation of C6H6O^+cations has not been reported in literature.The insight into the benzene oxidation reactions derived from the gas-phase model systems is helpful to build a detailed picture of oxidative mechanisms of C6H6 and its derivatives over corresponding mineral oxide aerosols.
基金supported by the National Natural Science Foundation of China(No.32101153)the Fundamental Research Funds for the Central Universities(No.2021CX11018).
文摘Photoacoustic imaging(PAI)is a new biomedical imaging technology that provides a mixed contrast mechanism and excellent spatial resolution in biological tissues.It is a non-invasive technology that can provide in vivo anatomical and functional information.This technology has great application potential in microscopic imaging and endoscope system.In recent years,the devel-opment of micro electro mechanical system(MEMS)technology has promoted the improvement and miniaturization of the photoacoustic imaging system,as well as its preclinical and clinical appli-cations.This paper introduces the research progress of MEMS technology in photoacoustic micro-scope systems and the miniaturization of photoacoustic endoscope ultrasonic transducers,and points out the shortcomings of existing technology and the direction of future development.
基金Project supported by the Nanhu Scholars Program for Young Scholars of Xinyang Normal University
文摘The space-confined synthesis method has been an efficient way for the preparation of linear carbon chains.However,the large-scale preparation of linear carbon chains still faces many challenges due to the lack of methods for the large-scale synthesis of precursors,such as short carbon chains(polyynes),and regulation technology for the transport of reactants in one-dimensional space.Here,we report a facile method for the rapid preparation of polyynes in large quantities using a commercial laser marking machine.Spectroscopic characterizations show that a large number of polyynes,such as C_(8)H_(2),C_(10)H_(2),C_(12)H_(2),and C_(14)H_(2),can be produced by ablating the graphite plate immersed in the organic liquid using a laser marking machine.The results of in situ Raman spectroscopy investigation of C_(2n)H_(2)-filled single-walled carbon nanotubes further confirm that a variety of polyyne molecules are synthesized.Meanwhile,in situ Raman spectroscopy also shows that the local heating treatment can accelerate the filling process of C_(2n)H_(2)into one-dimensional channels.This work provides new insights into the study of linear carbon chains and space-confined synthesis methods.
基金supported financially by the National Natural Science Foundation of China(No.32172197)the Innovative Project of the State Key Laboratory of Food Science and Technology(SKLF-ZZB-202307)the program of“Collaborative Innovation Center of Food Safety and Quality Control in Jiangsu Province”,China.
文摘In this study,Cicada chrysalis protein(CCP)was enzymatically hydrolyzed using alkaline protease 6L,followed by ultrafiltration and preparative high-performance liquid chromatography(prep-HPLC)for fractionation.The optimal peptide fractions were identified through nano-HPLC-MS/MS,leading to the discovery of four novel angiotensin-converting enzyme(ACE)inhibitory peptides:FRGF,SPRPW,GPKLF,and SYRF.The IC50 values for these peptides were determined to be 1.716 mg/mL,0.34 mg/mL,0.118 mg/mL,and 0.026 mg/mL,respectively.Molecular interaction analysis revealed that these peptides primarily bind to key residues within the ACE active site via hydrogen bonding.Isothermal titration calorimetry(ITC)further confirmed the binding of all peptides to the ACE active site,revealing a compensatory relationship between entropy and enthalpy during the binding process.Notably,GPKLF and SYRF were shown to significantly increase nitric oxide(NO)production in human umbilical vein endothelial cells(HUVECs)while reducing endothelin-1(ET-1)secretion.By inhibiting the ACE/AT1R axis and ET-1 expression,while simultaneously activating the ACE2/Ang1-7 axis and NO signaling pathway,these bioactive peptides help restore the balance of the renin-angiotensin system and enhance endothelial function,thereby exerting their protective effects on cardiovascular health.The results of this study suggest that CPP may serve as a promising source of ACE inhibitory peptides,offering a theoretical foundation for the development of functional foods with antihypertensive properties.
基金supported financially by the National Natural Science Foundation of China(No.32172197,32272314)program of“Collab-orative Innovation Center of Food Safety and Quality Control in Jiangsu Province”,China.
文摘The speciation of Se varies among different plants.Predominant Se species in the protein digestion products of Cardamine violifolia(H-CVP),soybean(H-SBP),and cabbage(H-CBP)are SeCys_(2),SeMet,and Se(VI),respec-tively.This study aims to elucidate the neuroprotective effects,bioavailability and transport mechanism of Se in Se-enriched proteins with different Se species.Compared to low-Se protein digestion products,Se-enriched protein digestion products significantly reduced Aβ_(1-42) induced apoptosis in PC-12 cells at the same protein matrix,especially H-CVP(increased by 32.4%relative to the control group).These results indicated that Se enrichment significantly enhances the neuroprotective effects of plant-derived proteins.In addition,H-SBP exerted neuroprotective effects by reducing caspase-9 activity by 42%,whereas H-CVP significantly decreased caspase-3 activity by 29%.The bioavailability of total Se in H-CVP,H-SBP and H-CBP were 29.07%,44.90%and 26.11%,respectively.Se species might also influence the bioavailability of Se,thereby affecting its neuro-protective activity.Furthermore,the transport of the three Se-enriched proteins was energy-dependent and some active transport carriers may be involved in their transmembrane transport.The novel organic cation and plasma membrane monoamine transporter families were participated the absorption of Se while multidrug resistance related protein families regulated the effluxion of Se in H-SBP and H-CVP group.For the H-CBP,organic anion transporters and P-protein families influenced the absorption and effluxion of Se.This study provides a basis for further studies on the roles of different Se species in the neuroprotective effects and bioavailability of Se-enriched proteins.
基金supported financially by the National Natural Science Foundation of China(No.32172197,32272314)program of“Collaborative Innovation Center of Food Safety and Quality Control in Jiangsu Province”,China.
文摘Epigallocatechin-3-gallate(EGCG)is a natural polyphenol with potent antioxidant and anticancer activities;however,its biomedical application is hindered by poor stability and high susceptibility to environmental degradation.In this study,we employed Mannich condensation reaction between EGCG and selenocystine(SeCys_(2))to construct EGCG-based nanoparticles(ESNPs)in aqueous media for tumor inhibition.FTIR,^(1)H NMR,and STEM analyses verified that ESNPs possessed a robust cross-linked three-dimensional network architecture,characterized by C-O-C,C-N-C,and C-Se-C bonds.The resulting ESNPs exhibited uniform spherical morphology,improved colloidal stability,and homogeneous selenium(Se)distribution.Cellular assays revealed that ESNPs were efficiently internalized by Hepa1-6 and SCC-7 cells and predominantly accumulated in the perinuclear region,where they induced pronounced oxidative stress,lipid peroxidation,DNA damage,and subsequent apoptosis.ESNPs displayed substantially enhanced anti-tumor activity against PC12,Hepa1-6,SCC-7,and LLC cells,yielding IC_(50)values of 24.77,18.71,34.04,and 34.96μg/mL,respectively,significantly lower than those of free EGCG,SeCys2,or their physical mixture.Notably,ESNPs exhibited reduced toxicity toward normal C2C12 cells,demonstrating favorable tumor selectivity.Overall,this work presents a simple and green strategy for the construction of natural polyphenol-Se hybrid nanoparticles with synergistic redox regulation and apoptosis-inducing capabilities.
基金the National Natural Science Foundation of China(No.22105079)Natural Science Foundation of Guangdong Province(No.2023B1515130004)+1 种基金Guangdong Basic and Applied Basic Research Natural Science Funding(Nos.2023A1515010849 and 2024A1515012328)Key-Area Research and Development Program of Guangdong Province(No.2024B1111080003)。
文摘Garnet-type ceramic Li-La_(3)Zr_(2)O_(12)(LLZO)stands out as a potential solid-state electrolyte,offering a promising alternative to conventional flammable liquid electrolytes.However,its large interfacial resistance with electrodes remains a significant challenge.In this research,we have successfully in-situ fabricated polymeric interface layers on both cathode and anode sides with LLZO.By tuning the gel-polymer interphase via fluoroethylene carbonate(FEC),known as FGPE,we have established a rapid Li^(+) transport channel by enhancing the solid-solid interfacial contact.This FGPE layer exhibits exceptional ionic conductivity of 1.38 mS/cm and a high Li-ion transference number of 0.64.Furthermore,FGPE effectively mitigates concentration polarization under high currents,thereby enabling a higher capacity output.In comparison to gel-polymer interphases with dimethyl carbonate(DMC)as the solvent(referred to as GPE),the Li|FGPE|Li symmetrical cell has demonstrated superior stability in plating/strapping performance over800h at a current density of 0.1 mA/cm^(2).Moreover,the Li|FGPE|LLZO|FGPE|LiFePO_(4) cell has exhibited commendable rate capability and has maintained a high capacity retention of 98.94%at 0.5 C after 200cycles.This study underscores an innovative approach in advancing in field of solid-state batteries,anticipated to be broadly applicable to other solid-state batteries by facilitating an abundance of robust solid-solid interfacial contacts.
基金National Natural Science Foundation of China(No.22379111,22179093,52473287)Key Research Project of Shenzhen(KCXFZ20240903094159005)+1 种基金Fund of the Department of Education of Guangdong Province for Higher Educational Institution(No.2022ZDZX4104,2024KCXTD064)Shenzhen General Project for Institutions of Higher Education(No.20231127113219001).
文摘Electrocatalytic ammonia oxidation reaction(AOR)represents a sustainable synthesis approach for valuable nitrogen‑containing compounds like nitrites and nitrates.However,the numerous AOR intermediates often complicate the precise regulation of target intermediate adsorption,hindering the efficient and selective nitrate/nitrite production.We herein present a NiCu‑BDC MOF with tunable AOR product selectivity,which undergoes a controllable in situ reconstruction into Cu‑β‑NiOOH at 1.7 V vs.RHE,enabling the shift of the reaction pathway from NH_(4)^(+)‑to‑NO_(2)^(−)to NH_(4)^(+)‑to‑NO_(3)^(−).The unique restructuring behavior of this material,combined with its dense active sites,enables highly selective production of nitrites and nitrates(94.9%NO_(2)^(−)selectivity at 1.60 V vs.RHE and 92.6%NO_(3)^(−)selectivity at 1.95 V vs.RHE).Theoretical simulations reveal that the Cu incorporation in NiCu‑BDC modulates the electronic configuration of Ni sites,facilitating moderate adsorption of key NO and NOOH intermediates,thus promoting efficient nitrite generation at low potentials.At higher potentials,NiCu‑BDC undergoes reconstruction to Cu‑β‑NiOOH,stabilizing the conversion of NO_(2)to NO_(2)OH,making nitrate formation thermodynamically favorable and a rapid selectivity shift.This potential‑driven selectivity control not only provides a new strategy for efficient nitrites/nitrates synthesis by simply adjusting applied potentials but also provides fundamental insights into regulating selectivity in multi‑product electrochemical reactions.
基金supported by the National Key R&D Program of China(No.2022YFB4601300)Aeronautical Science Fund(No.3030021252404)+2 种基金the National Natural Science Foundation of China(NSFC,No.52475425)the NSFC Basic Sciences Center Program(Extreme Light Field Manufacturing,No.52488301)We thank the Analytical&Testing Center of Beijing Institute of Technology for providing XPS and valence band measurements.We thank the BL02B01 and BL01B Beamlines at Shanghai Synchrotron Radiation Facility(SSRF),supported by the NSFC(No.11227902),for photoelectron spectroscopy and vibrational spectroscopy studies.We thank the support from beamline BL11U and BL10B at the National Synchrotron Radiation Laboratory(NSRL)in Hefei,China,for the synchrotron radiation and X-ray spectroscopic measurements.
文摘The electrochemical conversion of CO_(2) into value-added chemicals presents an environmentally sustainable alternative to conventional fossil-derived processes,yet achieving high selectivity remains challenging due to competing reaction pathways.Here,we demonstrate precise tuning of CO_(2) electroreduction pathways through femtosecond laser-driven surface doping of Cu with targeted metals,achieving Faradaic efficiencies of 58.9%for CO,67.9%for formate,and 37.8%for ethylene.This spatially shaping laser technique enables nanoscale deposition of any metal(including Sb,Sn,Re,La,In,Co,Ni,Ag,and Pt)onto Cu foil,forming compositionally graded Cu-based bimetallic surfaces with controlled atomic ratios.Systematic electronic structure analysis reveals that secondary metals induce d-band center shifts spanning−0.21 to+0.78 eV,governing intermediate adsorption energetics-upward shifts strengthen*CO binding via enhanced back-donation,while downward shifts generally weaken adsorbate interactions.Through precise control of Cu/Sn and Cu/Sb atomic ratios,we manipulate electronic structures of CuSn and CuSb catalysts and consequently demonstrate continuous tuning of formate(19.0%-67.9%)and CO(18.8%-58.9%)selectivity.In-situ Raman spectroscopy and valence band X-ray photoelectron spectroscopy(XPS)elucidate dual modulation mechanisms.Sn enhances CO desorption by weakening*CO adsorption,whereas La promotes ethylene formation through optimized CO absorption and dimerization.The tunability of the reaction pathways aligns with metal-dependent stabilization of critical intermediates(CO and*OCHO).This work introduces a nanoscale-depth and trace-level multi-elemental loading strategy with tunable ratios on copper electrodes,enabling precise electronic structure manipulation of Cu-based electrocatalysts to mechanistically elucidate the correlation between surface electronic states and product selectivity,offering a roadmap to design and modulate Cu-based catalysts for selective CO_(2)-to-chemical conversion and beyond via low-cost laser processing techniques.
基金supported by the National Natural Science Foundation of China(NSFC),Basic Sciences Center Program(Extreme Light Field Manufacturing,No.52488301)and NSFC General Program(No.52475425)the National Key R&D Program of China(No.2022YFB4601300)Aeronautical Science Fund(No.3030021252404).
文摘Elucidation of a physicochemical process on nanocatalysts,especially under continuously evolving conditions,is often heavily tool-driven because of technical challenges.Recently,ambient pressure X-ray photoelectron spectroscopy(APXPS)emerges as an emerging photon-in-electron-out technique in in-situ/operando analysis by bridging the pressure-gap between conventional ultra-high vacuum(UHV)and near ambient or even close to operating conditions,rendering the advancement of XPS from a UHV-based technique to a versatile and powerful tool that enables the specific probe of numerous events taking place at the gas–solid,liquid–solid and liquid–gas nanoscale interfaces which are critical to nanocatalysis research.For example,APXPS probes information on catalytically active phase and reaction kinetics in nanocatalytic processes;details inside the electric double-layer at an electrolyte/electrode interface can now be accessed;more efficient nanocatalyst design can be achieved and energy transfer venues can be optimized.Here,we aim to critically review the recent advances in instrumentation and the probe of the gas–solid,liquid–solid,and gas–liquid nanoscale interfaces using APXPS-based methodologies,followed by putting forward an outlook of development of APXPS as a rising in-situ/operando analytical means in surface science,nanocatalysis,nanoscience materials science.
基金supported by the National Natural Science Foundation of China (21573083)the Fundamental Research Funds for the Central Universities (2019kfy RCPY100)
文摘Developing facile methods to construct hierarchical-structured transition metal phosphides is beneficial for achieving high-efficiency hydrogen evolution catalysts.Herein,a self-template strategy of hydrothermal treatment of solid Ni-Co glycerate nanospheres followed by phosphorization is delivered to synthesize hierarchical Ni Co P hollow nanoflowers with ultrathin nanosheet assembly.The microstructure of Ni Co P can be availably tailored by adjusting the hydrothermal treatment temperature through affecting the hydrolysis process of Ni-Co glycerate nanospheres and the occurred Kirkendall effect.Benefitting from the promoted exposure of active sites and affluent mass diffusion routes,the HER performance of the Ni Co P hollow nanoflowers has been obviously enhanced in contrast with the solid Ni Co P nanospheres.The fabricated Ni Co P hollow nanoflowers yield the current density of 10 m A cmà2at small overpotentials of 95 and 127 m V in 0.5 mol Là1H2SO4and 1.0 mol Là1KOH solution,respectively.Moreover,the two-electrode alkaline cell assembled with the Ni Co P and Ir/C catalysts exhibits sustainable stability for overall water splitting.The work provides a simple but efficient method to regulate the microstructure of transition metal phosphides,which is helpful for achieving high-performance hydrogen evolution catalysts based on solid-state metal alkoxides.
