Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and effic...Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and efficient energy technologies,are constrained in their performance enhancement by the sluggish oxygen reduction reaction(ORR)kinetics at the cathode,anode CO poisoning(e.g.,from methanol crossover)and intricate water management dilemmas[1].展开更多
We successfully incorporated phenyl groups into a small-molecule quaternary ammonium cross-linker and synthesized cross-linked polybenzimidazole membranes via a one-step cross-linking process.Compared with conventiona...We successfully incorporated phenyl groups into a small-molecule quaternary ammonium cross-linker and synthesized cross-linked polybenzimidazole membranes via a one-step cross-linking process.Compared with conventional quaternary ammonium-crosslinked benzimidazole membranes,the introduction of phenyl groups significantly increases the free volume within the membrane.After phosphoric acid doping,the benzimidazole membrane with larger free volume retains more phosphoric acid compared to conventional quaternary ammonium-crosslinked membranes,forming an extensive hydrogen-bonding network that effectively enhances its anhydrous proton conductivity.The anhydrous proton conductivity reaches 91 mS·cm^(-1)at 160℃,substantially higher than that of conventional quaternary ammonium-crosslinked membranes with the same mass fraction.Benefiting from the improved conductivity,the membrane electrode assembly exhibits reduced ohmic polarization,achieving a peak power density of 792 mW·cm^(-2)at 160℃.展开更多
Proton exchange membranes(PEMs)play a central role in determining the efficiency,durability,and operational flexibility of PEM fuel cells(PEMFCs).However,conventional PEMs exhibit strong temperature-dependent proton-t...Proton exchange membranes(PEMs)play a central role in determining the efficiency,durability,and operational flexibility of PEM fuel cells(PEMFCs).However,conventional PEMs exhibit strong temperature-dependent proton-transport behavior,which limits their ability to support both rapid start-up at low temperatures and stable operation at elevated temperatures.Water-mediated PEMs show excellent conductivity under low-temperature and high-humidity conditions but suffer from dehydration and structural instability in the high-temperature regime.In contrast,water-independent PEMs,particularly phosphoric-acid-doped systems,conduct protons efficiently under anhydrous high-temperature conditions yet experience acid leaching that hampers room-temperature start-up and long-term durability.This review summarizes the fundamental proton-transport mechanisms that govern temperature-dependent performance and discusses recent advances in materials design aimed at enabling wide-temperature-range PEM operation.For water-mediated membranes,strategies such as incorporating hydrophilic fillers,constructing confined hydrophilic domains,and introducing additional proton-transfer sites have been developed to mitigate water loss and stabilize proton conduction.For water-independent membranes,approaches including strengthening polymer–acid interactions,engineering nanoscale confinement,designing multilayer architectures,and constructing multi–proton-carrier networks effectively improve acid retention and broaden operational temperature windows.Emerging fixed-carrier systems based on phosphonic-acid-grafted polymers,metal–organic frameworks,and covalent organic frameworks offer new pathways for stable anhydrous proton conduction across a wide temperature range.We conclude by outlining key challenges and future research opportunities,including reducing the dependence on volatile or leachable proton carriers,developing adaptive nanochannel architectures,improving anhydrous high-temperature conduction,and establishing scalable membrane fabrication methods.Continued innovation in these directions is expected to enable next-generation wide-temperature-range PEMs capable of flexible,high-efficiency operation from sub-zero to high-temperature conditions.展开更多
Introduction-Nuclei near and beyond the proton drip line represent a fascinating frontier in the nuclear landscape. Proton-rich nuclei exhibit intriguing phenomena, such as the Thomas-Ehrman shift and proton-halo stru...Introduction-Nuclei near and beyond the proton drip line represent a fascinating frontier in the nuclear landscape. Proton-rich nuclei exhibit intriguing phenomena, such as the Thomas-Ehrman shift and proton-halo structure. Beyond the proton dripline, nuclei become unbound, allowing protons to be emitted and giving rise to novel radioactive decay modes. Single-proton radioactivity, a process in which some nuclei with an odd number of protons(Z) decay by ejecting a proton, was discovered several decades ago and has been extensively studied [1, 2].展开更多
This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the correspo...This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.展开更多
Proton exchange membrane fuel cells(PEMFCs)are considered as a promising renewable power source.However,the massive commercial application of PEMFCs has been greatly hindered by their high expense and less-satisfied p...Proton exchange membrane fuel cells(PEMFCs)are considered as a promising renewable power source.However,the massive commercial application of PEMFCs has been greatly hindered by their high expense and less-satisfied performance mainly due to the sluggish oxygen reduction reaction(ORR)kinetics even on state-of-the-art Pt catalyst.Octahedral PtNi nanoparticles(oct-PtNi NPs)with excellent ORR activity in a half-cell have been widely studied,while their performance in membrane electrode assembly(MEA)has much less reported.Herein,we investigated the MEA performance using the carbon supported oct-PtNi NPs(oct-PtNi/C)as the cathode catalyst.Under the mild acid washing condition,the surface Ni atoms of oct-PtNi/C were largely removed,and the performance of the MEA using the acid-leaching oct-PtNi/C(PNC-A)as the cathode catalyst was greatly improved.The maximum power density of the MEA reached 1.0 W·cm^(-2) with the cath-ode Pt loading of 0.2 mg·cm^(-2),which is 15%higher than that using Pt/C as the catalyst.After 30k cycles in the accelerated degradation test(ADT),the MEA using PNC-A as the catalyst showed a performance retention of 82%,higher than that of Pt/C(74%).The results reported here verify the possibility of using PNC-A as an advanced cathode catalyst in PEMFCs,thus enhancing the performance of PEMFCs while lowering the amount of expensive Pt.展开更多
An important feature of quantum chromodynamics(QCD)is that the strong force grows as the distance between partons increases,which confines partons into hadrons,commonly known as QCD confinement.Perturbative QCD(pQCD)d...An important feature of quantum chromodynamics(QCD)is that the strong force grows as the distance between partons increases,which confines partons into hadrons,commonly known as QCD confinement.Perturbative QCD(pQCD)does not work at large distance,such as the length scale of a hadron,which is the regime of non-perturbative QCD.The detailed QCD mechanisms through which confinement occurs from partons to hadrons(usually known as hadronization),and how it manifests itself in partonic structure of hadrons(usually known as parton distribution),remain unresolved puzzles of first-principle QCD calculations.展开更多
This work presents a systematic analysis of proton-induced total ionizing dose(TID)effects in 1.2 k V silicon carbide(SiC)power devices with various edge termination structures.Three edge terminations including ring-a...This work presents a systematic analysis of proton-induced total ionizing dose(TID)effects in 1.2 k V silicon carbide(SiC)power devices with various edge termination structures.Three edge terminations including ring-assisted junction termination extension(RA-JTE),multiple floating zone JTE(MFZ-JTE),and field limiting rings(FLR)were fabricated and irradiated with45 Me V protons at fluences ranging from 1×10^(12) to 1×10^(14) cm^(-2).Experimental results,supported by TCAD simulations,show that the RA-JTE structure maintained stable breakdown performance with less than 1%variation due to its effective electric field redistribution by multiple P+rings.In contrast,MFZ-JTE and FLR exhibit breakdown voltage shifts of 6.1%and 15.2%,respectively,under the highest fluence.These results demonstrate the superior radiation tolerance of the RA-JTE structure under TID conditions and provide practical design guidance for radiation-hardened Si C power devices in space and other highradiation environments.展开更多
Proton-conducting oxides constitute a wide class of materials that exhibit pronounced proton transport in humid atmospheres.Owing to their high proton mobility,these oxides are regarded as promising electrolytes for l...Proton-conducting oxides constitute a wide class of materials that exhibit pronounced proton transport in humid atmospheres.Owing to their high proton mobility,these oxides are regarded as promising electrolytes for low-and intermediate-temperature protonic ceramic fuel cells and electrolysis cells,which offer efficient and clean energy conversion.Protons appear in complex oxides through a dissociative water adsorption process,which consists of the interaction between existing oxygen vacancies and water molecules in the gas phase.This process is also known as hydration or water uptake.Within the present work,we analyze the hydration features of BaSn_(1-x)In_(x)O_(3-δ)perovskite materials(BSIx),which include a wide range of solid solutions(0≤x<0.7)and a nearly theoretical hydration limit for almost all studied compounds at the same time.The latter is a unique property of In-doped stannates,which is untypical for most other proton-conducting oxides.Along with the experimental data on the water uptake of BSIx,we provide an in-depth investigation of proton concentrations depending on external factors,involving a further comparison with literature data on materials hydration,as well as the discovery of hidden relationships between proton concentration and various functional properties.Therefore,this work contributes to theoretical and applied investigations of proton-conducting oxides,especially in the context of their hydration behavior.展开更多
Currently,zinc anodes are facing problems such as the growth of zinc dendrites and the frequent occurrence of side reactions,while existing additive strategies are still challenging due to the poor stability of the ad...Currently,zinc anodes are facing problems such as the growth of zinc dendrites and the frequent occurrence of side reactions,while existing additive strategies are still challenging due to the poor stability of the adsorption layer and the ambiguous mechanisms of action.In this study,a highly stable Vani molecular brush additive was designed.The additive effectively inhibits H_(2) generation by targeting and anchoring H+in the inner Helmholtz layer,and reduces the water activity by constructing an enhanced hydrogen bonding network through the interaction with water molecules,thus inhibiting the parasitic side reactions on the zinc anode.In addition,the dynamic interfacial molecular layer can regulate and buffer the interfacial Zn^(2+)for highly reversible plating/stripping.Experiments show that the symmetric cell cycle life is as long as 3760 h at a Vani content of only 2×10^(-3) g L^(-1) with a current density of5 mA cm^(-2).The cycle life of the Zn‖MnO_(2) and Zn‖Zn_(0.58)V_(2)O_(5) H_(2)O full battery is significantly improved.This study deepens the understanding of the working mechanism of the zinc electrode interface and provides new ideas for non-sacrififcial trace additive design.展开更多
Clean energy devices have the potential to change the world and avoid future energy crises.The development of new energyefficient technologies helps reduce our dependence on limited fossil fuel resources.Hydrogen ener...Clean energy devices have the potential to change the world and avoid future energy crises.The development of new energyefficient technologies helps reduce our dependence on limited fossil fuel resources.Hydrogen energy is the key to achieving clean energy transition goals.Proton exchange membrane fuel cells play a critical role.Research and development of new hightech proton exchange membranes(PEMs)provide new horizons for the development of hydrogen energy.The use of carbon nanomaterials to improve PEM efficiency is one of the modern trends.The modification of modern membranes with fullerenes and their derivatives is an innovative strategy for increasing proton conductivity.This paper discusses the key principles of proton transport in PEMs modified with individual fullerenols,sulfofullerenes,carboxylated fullerenes,phosphofullerenes,and cianohydrofullerenes.The introduction of fullerene nanoparticles into polymer PEM induces an improvement in key properties.Summary information covers existing research on the use of fullerenes as nanoscale modifiers of proton-conducting materials.This review will help researchers to surpass the achieved results in the field of modern proton-conducting materials and stimulate the development of hydrogen energy.展开更多
Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve t...Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve the migration of a highly efficient hydrogen species to Pt sites over Pt/Co@NC,which is obtained through a facile calcination and electrodeposition method.It exhibits an outstanding geometric activity(η_(10)=31 m V),which surpasses the commercial 20 wt%Pt/C(η_(10)=37 mV).Moreover,the mass activity of Pt/Co@NC is 5.6 A mg_(Pt)^(-1) at-50 mV vs.RHE,which is 2.23 times higher than that of 20 wt%Pt/C.Experimental and theoretical results indicate that the work function of the outer carbon layer,which is changed by the introduction of the inner cobalt core,plays a crucial role in reversing the direction of electron migration between the carbon layer and Pt.The negatively charged Pt^(δ-)can spontaneously attract positively charged protons via the electrostatic interaction effect,thereby achieving the directional migration of hydrogen species.This work presents a strategy for designing advanced alkaline HER electrocatalysts by the electrostatic effect.展开更多
Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent ...Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent is investigated as an aqueous proton battery electrolyte,which not only enhances the cycling performance of MoO_(3) nanorod anode but also improves its low-temperature electrochemical performance.Specifically,the EG tightly adsorbs onto the surface of MoO_(3) nanorods,thereby inhibiting the corrosion from H_(2)O molecules in the electrolyte and suppressing the dissolution of MoO_(3).In addition,EG molecule disturbs the hydrogen-bond network between H_(2)O molecules,which greatly decreases the freezing point of the electrolyte,endowing the MoO_(3) nanorods with excellent low-temperature electrochemical performance.Therefore,the MoO_(3) nanorods exhibit a capacity retention of 96.9%after 2000 cycles at a current density of 10 A g^(-1)in a three-electrode system.After assembling with CuHCF cathode,under-40℃,the full battery displays negligible capacity decay for over 2500 cycles at 1 A g^(-1).These results indicate that the cosolvent strategy has the promising potential in enhancing the performance of aqueous proton batteries.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demons...Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.展开更多
Understanding the proton dynamic behavior in inorganic materials has long been a topic of intense fascination[1],especially in the field of electrochemical energy storage[2].One of the examples is the research of prot...Understanding the proton dynamic behavior in inorganic materials has long been a topic of intense fascination[1],especially in the field of electrochemical energy storage[2].One of the examples is the research of proton transport in transition metal oxides,which dates back to 1971[3]when RuO_(2) was discovered to be capable of storing protons via reversible redox reactions[4].In aqueous electrolytes,the thin film RuO_(2) electrode exhibits a surface pseudocapacitive behavior[5],which could be modified by the structural water in its hydrated form due to the facile Grotthuss hopping mode of protons along the established hydrogen bonds inside the bulk phase[6].Soon later,Goodenough et al.reported the capacitor-like behavior of amorphous MnO_(2)·xH_(2)O electrode in an aqueous KCl electrolyte[7],and further studies on the hydrated MnO_(2) electrodes prepared by sol-gel processes have soon discovered that the intercalation of protons from aqueous electrolytes plays an indispensable role in the charge storage mechanism[8].In recent years,the research interest on rechargeable aqueous batteries has fueled the renaissance of mechanistic study of proton transport in transition metal oxides[9],which can operate as cathodes or anodes via a topotactic insertion mechanism similar to that in Li-ion batteries[10].However,due to the challenges for experimental detection of local chemical environments of the inserted protons,a comprehensive understanding of proton dynamic behavior in these electrodes remains largely lacking.展开更多
The significance of laser-driven polarized beam acceleration has been increasingly recognized in recent years.We propose an efficient method for generating polarized proton beams from a pre-polarized hydrogen halide g...The significance of laser-driven polarized beam acceleration has been increasingly recognized in recent years.We propose an efficient method for generating polarized proton beams from a pre-polarized hydrogen halide gas jet,utilizing magnetic vortex acceleration enhanced by a laser-driven plasma bubble.When a petawatt laser pulse passes through a pre-polarized gas jet,a bubble-like ultra-nonlinear plasma wave is formed.As a portion of the particles constituting this wave,background protons are swept by the acceleration field of the bubble and oscillate significantly along the laser propagation axis.Some of the pre-accelerated protons in the plasma wave are trapped by the acceleration field at the rear side of the target.This acceleration field is intensified by the transverse expansion of the laser-driven magnetic vortex,resulting in energetic polarized proton beams.The spin of energetic protons is determined by their precession within the electromagnetic field,which is described using the Thomas-Bargmann-Michel-Telegdi equation in analytical models and particle-in-cell simulations.Multidimensional simulations reveal that monoenergetic proton beams with an energy of hundreds of MeV,a beam charge of hundreds of pC,and a beam polarization of tens of percent can be produced at laser powers of several petawatts.Such laser-driven polarized proton beams have promise for application in polarized beam colliders,where they can be utilized to investigate particle interactions and to explore the properties of matter under extreme conditions.展开更多
Proton exchange membrane water electrolysis(PEMWE)technology is widely recognized as a cornerstone for green hydrogen production,offering high operational current densities exceeding 1.0 A cm^(-2),rapid dynamic respon...Proton exchange membrane water electrolysis(PEMWE)technology is widely recognized as a cornerstone for green hydrogen production,offering high operational current densities exceeding 1.0 A cm^(-2),rapid dynamic response capabilities,and zero-carbon emission characteristics[1].However,the sluggish kinetics of oxygen evolution reaction(OER)at the anode presents a critical bottleneck for large-scale commercial deployment(Fig.1(a)).Despite significant advancements through electronic structure modulation[2]and coordination environment optimization[3],the deprotonation energy barrier of oxygen-containing intermediates and the stability of active sites under acidic conditions remain unresolved challenges.展开更多
“Three-in-one”cathode,achieved via B-site heavy-doping of transition elements(typically Co,Fe)into proton-conductive perovskite,holds promise for enhancing the performance of proton-conducting solid oxide fuel cell(...“Three-in-one”cathode,achieved via B-site heavy-doping of transition elements(typically Co,Fe)into proton-conductive perovskite,holds promise for enhancing the performance of proton-conducting solid oxide fuel cell(H-SOFC)operated below 650℃for electricity generation.However,its electrochemical behavior above 650℃,essential for improving the efficiency of H-SOFC for fuel conversion,remains insufficiently explored.It is still challenging to propose guidance for the design of“threein-one”cathode toward optimal H-SOFC performance below and above 650℃,with the prerequisite of gaining a comprehensive understanding of the roles of Co and Fe in determining the H-SOFC performance.This work is to address this challenge.Through theoretical/experimental studies,Co is identified to play a role in improving the oxygen reduction reaction(ORR)activity while Fe plays a role in facilitating the cathode/electrolyte interfacial proton conduction.Therefore,if the operating temperature is above 650℃,lowering the Co/Fe ratio in“three-in-one”cathode becomes crucial since the limiting factor shifts from ORR activity to proton conduction.Implementing this strategy,the SOFC using BaCo_(0.15)-Fe_(0.55)Zr_(0.1)Y_(0.1)Yb_(0.1)O_(3−δ)cathode achieves peak power densities of 1.67Wcm^(−2)under H-SOFC mode at 700℃and 2.32Wcm^(−2)under dual ion-conducting SOFC mode at 750℃,which are the highest reported values so far.展开更多
GaN diodes for high energy(64.8 MeV)proton detection were fabricated and investigated.A comparison of the performance of GaN diodes with different structures is presented,with a focus on sapphire and on GaN substrates...GaN diodes for high energy(64.8 MeV)proton detection were fabricated and investigated.A comparison of the performance of GaN diodes with different structures is presented,with a focus on sapphire and on GaN substrates,Schottky and pin diodes,and different active layer thicknesses.Pin diodes fabricated on a sapphire substrate are the best choice for a GaN proton detector working at 0 V bias.They are sensitive(minimum detectable proton beam<1 pA/cm^(2)),linear as a function of proton current and fast(<1 s).High proton current sensitivity and high spatial resolution of GaN diodes can be exploited in the future for proton imaging of patients in proton therapy.展开更多
We put forward a new design of a compact beam transport system for intense laser-driven proton therapy,where instead of using conventional pulsed solenoids,our design relies on a helical coil irradiated by a nanosecon...We put forward a new design of a compact beam transport system for intense laser-driven proton therapy,where instead of using conventional pulsed solenoids,our design relies on a helical coil irradiated by a nanosecond laser pulse to generate strong magnetic fields for focusing protons.A pair of dipole magnets and apertures are employed to further filter protons with large divergences and low energies.Our numerical studies combine particle-in-cell simulations for laser-plasma interaction to generate high-energy monoenergetic proton beams,finite element analysis for evaluating the magnetic field distribution inside the coil,and MonteCarlo simulations for beam transport and energy deposition.Our results show that with this design,a spread-out Bragg peak in a range of several centimeters to a deep-seated tumor with a dose of approximately 16.5 cGy and fluctuation around 2% can be achieved.The instantaneous dose rate reaches up to 10^(9)Gy/s,holding the potential for future FLASH radiotherapy research.展开更多
文摘Covalent organic framework ionomers enable synergistic efficient transport of protons and oxygen in medium-temperature proton exchange membrane fuel cells Proton exchange membrane fuel cells(PEMFCs),as clean and efficient energy technologies,are constrained in their performance enhancement by the sluggish oxygen reduction reaction(ORR)kinetics at the cathode,anode CO poisoning(e.g.,from methanol crossover)and intricate water management dilemmas[1].
基金Funded in part by the National Key Research and Development Program of China(No.2023YFB4006302)。
文摘We successfully incorporated phenyl groups into a small-molecule quaternary ammonium cross-linker and synthesized cross-linked polybenzimidazole membranes via a one-step cross-linking process.Compared with conventional quaternary ammonium-crosslinked benzimidazole membranes,the introduction of phenyl groups significantly increases the free volume within the membrane.After phosphoric acid doping,the benzimidazole membrane with larger free volume retains more phosphoric acid compared to conventional quaternary ammonium-crosslinked membranes,forming an extensive hydrogen-bonding network that effectively enhances its anhydrous proton conductivity.The anhydrous proton conductivity reaches 91 mS·cm^(-1)at 160℃,substantially higher than that of conventional quaternary ammonium-crosslinked membranes with the same mass fraction.Benefiting from the improved conductivity,the membrane electrode assembly exhibits reduced ohmic polarization,achieving a peak power density of 792 mW·cm^(-2)at 160℃.
基金supported by the National Natural Science Foundation of China(52277225)the Fundamental Research Funds for the Central Universities(xtr052024009).
文摘Proton exchange membranes(PEMs)play a central role in determining the efficiency,durability,and operational flexibility of PEM fuel cells(PEMFCs).However,conventional PEMs exhibit strong temperature-dependent proton-transport behavior,which limits their ability to support both rapid start-up at low temperatures and stable operation at elevated temperatures.Water-mediated PEMs show excellent conductivity under low-temperature and high-humidity conditions but suffer from dehydration and structural instability in the high-temperature regime.In contrast,water-independent PEMs,particularly phosphoric-acid-doped systems,conduct protons efficiently under anhydrous high-temperature conditions yet experience acid leaching that hampers room-temperature start-up and long-term durability.This review summarizes the fundamental proton-transport mechanisms that govern temperature-dependent performance and discusses recent advances in materials design aimed at enabling wide-temperature-range PEM operation.For water-mediated membranes,strategies such as incorporating hydrophilic fillers,constructing confined hydrophilic domains,and introducing additional proton-transfer sites have been developed to mitigate water loss and stabilize proton conduction.For water-independent membranes,approaches including strengthening polymer–acid interactions,engineering nanoscale confinement,designing multilayer architectures,and constructing multi–proton-carrier networks effectively improve acid retention and broaden operational temperature windows.Emerging fixed-carrier systems based on phosphonic-acid-grafted polymers,metal–organic frameworks,and covalent organic frameworks offer new pathways for stable anhydrous proton conduction across a wide temperature range.We conclude by outlining key challenges and future research opportunities,including reducing the dependence on volatile or leachable proton carriers,developing adaptive nanochannel architectures,improving anhydrous high-temperature conduction,and establishing scalable membrane fabrication methods.Continued innovation in these directions is expected to enable next-generation wide-temperature-range PEMs capable of flexible,high-efficiency operation from sub-zero to high-temperature conditions.
文摘Introduction-Nuclei near and beyond the proton drip line represent a fascinating frontier in the nuclear landscape. Proton-rich nuclei exhibit intriguing phenomena, such as the Thomas-Ehrman shift and proton-halo structure. Beyond the proton dripline, nuclei become unbound, allowing protons to be emitted and giving rise to novel radioactive decay modes. Single-proton radioactivity, a process in which some nuclei with an odd number of protons(Z) decay by ejecting a proton, was discovered several decades ago and has been extensively studied [1, 2].
文摘This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.
基金supported by grants from the Natural Science Foundation of China(22362031 and 21805121)the Science and Technology Project of Yunnan Province(2019FD137)。
文摘Proton exchange membrane fuel cells(PEMFCs)are considered as a promising renewable power source.However,the massive commercial application of PEMFCs has been greatly hindered by their high expense and less-satisfied performance mainly due to the sluggish oxygen reduction reaction(ORR)kinetics even on state-of-the-art Pt catalyst.Octahedral PtNi nanoparticles(oct-PtNi NPs)with excellent ORR activity in a half-cell have been widely studied,while their performance in membrane electrode assembly(MEA)has much less reported.Herein,we investigated the MEA performance using the carbon supported oct-PtNi NPs(oct-PtNi/C)as the cathode catalyst.Under the mild acid washing condition,the surface Ni atoms of oct-PtNi/C were largely removed,and the performance of the MEA using the acid-leaching oct-PtNi/C(PNC-A)as the cathode catalyst was greatly improved.The maximum power density of the MEA reached 1.0 W·cm^(-2) with the cath-ode Pt loading of 0.2 mg·cm^(-2),which is 15%higher than that using Pt/C as the catalyst.After 30k cycles in the accelerated degradation test(ADT),the MEA using PNC-A as the catalyst showed a performance retention of 82%,higher than that of Pt/C(74%).The results reported here verify the possibility of using PNC-A as an advanced cathode catalyst in PEMFCs,thus enhancing the performance of PEMFCs while lowering the amount of expensive Pt.
基金supported in part by the National Natural Science Foundation of China(No.12575145)the National Key Research and Development Program of China(No.2022YFA1604900)。
文摘An important feature of quantum chromodynamics(QCD)is that the strong force grows as the distance between partons increases,which confines partons into hadrons,commonly known as QCD confinement.Perturbative QCD(pQCD)does not work at large distance,such as the length scale of a hadron,which is the regime of non-perturbative QCD.The detailed QCD mechanisms through which confinement occurs from partons to hadrons(usually known as hadronization),and how it manifests itself in partonic structure of hadrons(usually known as parton distribution),remain unresolved puzzles of first-principle QCD calculations.
基金supported by the IITP(Institute for Information&Communications Technology Planning&Evaluation)under the ITRC(Information Technology Research Center)support program(IITP-2025-RS-2024-00438288)grant funded by the Korea government(MSIT)+1 种基金National Research Council of Science&Technology(NST)grant by the MSIT(Aerospace Semiconductor Strategy Research Project No.GTL25051-000)supported by the IC Design Education Center(IDEC),Korea。
文摘This work presents a systematic analysis of proton-induced total ionizing dose(TID)effects in 1.2 k V silicon carbide(SiC)power devices with various edge termination structures.Three edge terminations including ring-assisted junction termination extension(RA-JTE),multiple floating zone JTE(MFZ-JTE),and field limiting rings(FLR)were fabricated and irradiated with45 Me V protons at fluences ranging from 1×10^(12) to 1×10^(14) cm^(-2).Experimental results,supported by TCAD simulations,show that the RA-JTE structure maintained stable breakdown performance with less than 1%variation due to its effective electric field redistribution by multiple P+rings.In contrast,MFZ-JTE and FLR exhibit breakdown voltage shifts of 6.1%and 15.2%,respectively,under the highest fluence.These results demonstrate the superior radiation tolerance of the RA-JTE structure under TID conditions and provide practical design guidance for radiation-hardened Si C power devices in space and other highradiation environments.
文摘Proton-conducting oxides constitute a wide class of materials that exhibit pronounced proton transport in humid atmospheres.Owing to their high proton mobility,these oxides are regarded as promising electrolytes for low-and intermediate-temperature protonic ceramic fuel cells and electrolysis cells,which offer efficient and clean energy conversion.Protons appear in complex oxides through a dissociative water adsorption process,which consists of the interaction between existing oxygen vacancies and water molecules in the gas phase.This process is also known as hydration or water uptake.Within the present work,we analyze the hydration features of BaSn_(1-x)In_(x)O_(3-δ)perovskite materials(BSIx),which include a wide range of solid solutions(0≤x<0.7)and a nearly theoretical hydration limit for almost all studied compounds at the same time.The latter is a unique property of In-doped stannates,which is untypical for most other proton-conducting oxides.Along with the experimental data on the water uptake of BSIx,we provide an in-depth investigation of proton concentrations depending on external factors,involving a further comparison with literature data on materials hydration,as well as the discovery of hidden relationships between proton concentration and various functional properties.Therefore,this work contributes to theoretical and applied investigations of proton-conducting oxides,especially in the context of their hydration behavior.
基金supported by the Heilongjiang Province“Double First Class”Discipline Collaborative Innovation Project(LJGXCG2023-061)。
文摘Currently,zinc anodes are facing problems such as the growth of zinc dendrites and the frequent occurrence of side reactions,while existing additive strategies are still challenging due to the poor stability of the adsorption layer and the ambiguous mechanisms of action.In this study,a highly stable Vani molecular brush additive was designed.The additive effectively inhibits H_(2) generation by targeting and anchoring H+in the inner Helmholtz layer,and reduces the water activity by constructing an enhanced hydrogen bonding network through the interaction with water molecules,thus inhibiting the parasitic side reactions on the zinc anode.In addition,the dynamic interfacial molecular layer can regulate and buffer the interfacial Zn^(2+)for highly reversible plating/stripping.Experiments show that the symmetric cell cycle life is as long as 3760 h at a Vani content of only 2×10^(-3) g L^(-1) with a current density of5 mA cm^(-2).The cycle life of the Zn‖MnO_(2) and Zn‖Zn_(0.58)V_(2)O_(5) H_(2)O full battery is significantly improved.This study deepens the understanding of the working mechanism of the zinc electrode interface and provides new ideas for non-sacrififcial trace additive design.
基金supported by the Russian Science Foundation Project(23-13-00328)。
文摘Clean energy devices have the potential to change the world and avoid future energy crises.The development of new energyefficient technologies helps reduce our dependence on limited fossil fuel resources.Hydrogen energy is the key to achieving clean energy transition goals.Proton exchange membrane fuel cells play a critical role.Research and development of new hightech proton exchange membranes(PEMs)provide new horizons for the development of hydrogen energy.The use of carbon nanomaterials to improve PEM efficiency is one of the modern trends.The modification of modern membranes with fullerenes and their derivatives is an innovative strategy for increasing proton conductivity.This paper discusses the key principles of proton transport in PEMs modified with individual fullerenols,sulfofullerenes,carboxylated fullerenes,phosphofullerenes,and cianohydrofullerenes.The introduction of fullerene nanoparticles into polymer PEM induces an improvement in key properties.Summary information covers existing research on the use of fullerenes as nanoscale modifiers of proton-conducting materials.This review will help researchers to surpass the achieved results in the field of modern proton-conducting materials and stimulate the development of hydrogen energy.
基金financially supported by the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(23KJB610003)the Natural Science Foundation of Jiangsu Province(BK20240339)+2 种基金the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China(No.2023KJ104)the National Natural Science Foundation of China(No.52202092)the Natural Science Foundation of Shandong Province(No.ZR2022QE076)。
文摘Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve the migration of a highly efficient hydrogen species to Pt sites over Pt/Co@NC,which is obtained through a facile calcination and electrodeposition method.It exhibits an outstanding geometric activity(η_(10)=31 m V),which surpasses the commercial 20 wt%Pt/C(η_(10)=37 mV).Moreover,the mass activity of Pt/Co@NC is 5.6 A mg_(Pt)^(-1) at-50 mV vs.RHE,which is 2.23 times higher than that of 20 wt%Pt/C.Experimental and theoretical results indicate that the work function of the outer carbon layer,which is changed by the introduction of the inner cobalt core,plays a crucial role in reversing the direction of electron migration between the carbon layer and Pt.The negatively charged Pt^(δ-)can spontaneously attract positively charged protons via the electrostatic interaction effect,thereby achieving the directional migration of hydrogen species.This work presents a strategy for designing advanced alkaline HER electrocatalysts by the electrostatic effect.
基金supported by the National Natural Science Foundation of China(22409071)Natural Foundation of Shandong Province(ZR2024QB120)+2 种基金Youth Innovation Group Plan of Shandong Province(2024KJG046)Higher-Level Talent Initial Scientific Research and Discipline Construction Fund(511/1009530)Joint Funds of the National Natural Science Foundation of China(No.U22A20140)。
文摘Protons emerge as superior charge carriers due to the lowest mass-to-charge ratio,ultra-high natural abundance,and the smallest ionic radius.Herein,2.0 M H_(2) SO_(4) dissolved in EG(ethylene glycol)/H_(2)O cosolvent is investigated as an aqueous proton battery electrolyte,which not only enhances the cycling performance of MoO_(3) nanorod anode but also improves its low-temperature electrochemical performance.Specifically,the EG tightly adsorbs onto the surface of MoO_(3) nanorods,thereby inhibiting the corrosion from H_(2)O molecules in the electrolyte and suppressing the dissolution of MoO_(3).In addition,EG molecule disturbs the hydrogen-bond network between H_(2)O molecules,which greatly decreases the freezing point of the electrolyte,endowing the MoO_(3) nanorods with excellent low-temperature electrochemical performance.Therefore,the MoO_(3) nanorods exhibit a capacity retention of 96.9%after 2000 cycles at a current density of 10 A g^(-1)in a three-electrode system.After assembling with CuHCF cathode,under-40℃,the full battery displays negligible capacity decay for over 2500 cycles at 1 A g^(-1).These results indicate that the cosolvent strategy has the promising potential in enhancing the performance of aqueous proton batteries.
基金financially supported by the Natural Science Foundation of Shandong Province (No.ZR2022QE076)the National Natural Science Foundation of China (No.52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China (No.2023KJ104)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
基金financial support from the National Natural Science Foundation of China(22109003)the Basic and Applied Basic Research Foundation of Guangdong Province(2023A1515011391)+1 种基金Soft Science Research Project of Guangdong Province(No.2017B030301013)the Major Science and Technology Infrastructure Project of Material Genome Big-science Facilities Platform supported by Municipal Development and Reform Commission of Shenzhen.
文摘Understanding the proton dynamic behavior in inorganic materials has long been a topic of intense fascination[1],especially in the field of electrochemical energy storage[2].One of the examples is the research of proton transport in transition metal oxides,which dates back to 1971[3]when RuO_(2) was discovered to be capable of storing protons via reversible redox reactions[4].In aqueous electrolytes,the thin film RuO_(2) electrode exhibits a surface pseudocapacitive behavior[5],which could be modified by the structural water in its hydrated form due to the facile Grotthuss hopping mode of protons along the established hydrogen bonds inside the bulk phase[6].Soon later,Goodenough et al.reported the capacitor-like behavior of amorphous MnO_(2)·xH_(2)O electrode in an aqueous KCl electrolyte[7],and further studies on the hydrated MnO_(2) electrodes prepared by sol-gel processes have soon discovered that the intercalation of protons from aqueous electrolytes plays an indispensable role in the charge storage mechanism[8].In recent years,the research interest on rechargeable aqueous batteries has fueled the renaissance of mechanistic study of proton transport in transition metal oxides[9],which can operate as cathodes or anodes via a topotactic insertion mechanism similar to that in Li-ion batteries[10].However,due to the challenges for experimental detection of local chemical environments of the inserted protons,a comprehensive understanding of proton dynamic behavior in these electrodes remains largely lacking.
基金supported by the National Natural Science Foundation of China(Grant Nos.12075081 and 12404395)the Innovation Group Project of the Natural Science Foundation of Hubei Province of China(Grant No.2024AFA038)Bin Liu acknowledges the support of Guangdong High Level Innovation Research Institute Project,Grant No.2021B0909050006.
文摘The significance of laser-driven polarized beam acceleration has been increasingly recognized in recent years.We propose an efficient method for generating polarized proton beams from a pre-polarized hydrogen halide gas jet,utilizing magnetic vortex acceleration enhanced by a laser-driven plasma bubble.When a petawatt laser pulse passes through a pre-polarized gas jet,a bubble-like ultra-nonlinear plasma wave is formed.As a portion of the particles constituting this wave,background protons are swept by the acceleration field of the bubble and oscillate significantly along the laser propagation axis.Some of the pre-accelerated protons in the plasma wave are trapped by the acceleration field at the rear side of the target.This acceleration field is intensified by the transverse expansion of the laser-driven magnetic vortex,resulting in energetic polarized proton beams.The spin of energetic protons is determined by their precession within the electromagnetic field,which is described using the Thomas-Bargmann-Michel-Telegdi equation in analytical models and particle-in-cell simulations.Multidimensional simulations reveal that monoenergetic proton beams with an energy of hundreds of MeV,a beam charge of hundreds of pC,and a beam polarization of tens of percent can be produced at laser powers of several petawatts.Such laser-driven polarized proton beams have promise for application in polarized beam colliders,where they can be utilized to investigate particle interactions and to explore the properties of matter under extreme conditions.
基金financially supported by the Natural Science Foundation of Hunan Province(2023JJ40608,2024JJ6413)the Majoy Project of the Education Department of Hunan Province(24A0610).
文摘Proton exchange membrane water electrolysis(PEMWE)technology is widely recognized as a cornerstone for green hydrogen production,offering high operational current densities exceeding 1.0 A cm^(-2),rapid dynamic response capabilities,and zero-carbon emission characteristics[1].However,the sluggish kinetics of oxygen evolution reaction(OER)at the anode presents a critical bottleneck for large-scale commercial deployment(Fig.1(a)).Despite significant advancements through electronic structure modulation[2]and coordination environment optimization[3],the deprotonation energy barrier of oxygen-containing intermediates and the stability of active sites under acidic conditions remain unresolved challenges.
基金supported by the Natural Sciences and Engineering Research Council(NSERC)of Canada,Discovery Grant(GRPIN-2016-05494)Strategic Research Projects of Alberta Innovates Technology Futures(#G2016000655)funding from the Canada First Research Excellence Fund(CFREF-2015-00001).
文摘“Three-in-one”cathode,achieved via B-site heavy-doping of transition elements(typically Co,Fe)into proton-conductive perovskite,holds promise for enhancing the performance of proton-conducting solid oxide fuel cell(H-SOFC)operated below 650℃for electricity generation.However,its electrochemical behavior above 650℃,essential for improving the efficiency of H-SOFC for fuel conversion,remains insufficiently explored.It is still challenging to propose guidance for the design of“threein-one”cathode toward optimal H-SOFC performance below and above 650℃,with the prerequisite of gaining a comprehensive understanding of the roles of Co and Fe in determining the H-SOFC performance.This work is to address this challenge.Through theoretical/experimental studies,Co is identified to play a role in improving the oxygen reduction reaction(ORR)activity while Fe plays a role in facilitating the cathode/electrolyte interfacial proton conduction.Therefore,if the operating temperature is above 650℃,lowering the Co/Fe ratio in“three-in-one”cathode becomes crucial since the limiting factor shifts from ORR activity to proton conduction.Implementing this strategy,the SOFC using BaCo_(0.15)-Fe_(0.55)Zr_(0.1)Y_(0.1)Yb_(0.1)O_(3−δ)cathode achieves peak power densities of 1.67Wcm^(−2)under H-SOFC mode at 700℃and 2.32Wcm^(−2)under dual ion-conducting SOFC mode at 750℃,which are the highest reported values so far.
基金support from MATRIX(ANR-22-CE92-0047)with financial support from ITMI Cancer of Aviesan within the framework of the 2021−2030 Cancer Control Strategy,on funds administrated by INSERM through the project NECTAR.Matilde Siviero acknowledges funding from the French−German University/Saarbrücken(contract CDOC-06-2022).
文摘GaN diodes for high energy(64.8 MeV)proton detection were fabricated and investigated.A comparison of the performance of GaN diodes with different structures is presented,with a focus on sapphire and on GaN substrates,Schottky and pin diodes,and different active layer thicknesses.Pin diodes fabricated on a sapphire substrate are the best choice for a GaN proton detector working at 0 V bias.They are sensitive(minimum detectable proton beam<1 pA/cm^(2)),linear as a function of proton current and fast(<1 s).High proton current sensitivity and high spatial resolution of GaN diodes can be exploited in the future for proton imaging of patients in proton therapy.
基金supported by the National Key R&D Program of China(Nos.2022YFA1603200 and 2022YFA1603201)National Natural Science Foundation of China(Nos.12135001,11921006,12475243 and 11825502)+1 种基金Strategic Priority Research Program of CAS(No.XDA25050900)support from the National Natural Science Funds for Distinguished Young Scholar(No.11825502)。
文摘We put forward a new design of a compact beam transport system for intense laser-driven proton therapy,where instead of using conventional pulsed solenoids,our design relies on a helical coil irradiated by a nanosecond laser pulse to generate strong magnetic fields for focusing protons.A pair of dipole magnets and apertures are employed to further filter protons with large divergences and low energies.Our numerical studies combine particle-in-cell simulations for laser-plasma interaction to generate high-energy monoenergetic proton beams,finite element analysis for evaluating the magnetic field distribution inside the coil,and MonteCarlo simulations for beam transport and energy deposition.Our results show that with this design,a spread-out Bragg peak in a range of several centimeters to a deep-seated tumor with a dose of approximately 16.5 cGy and fluctuation around 2% can be achieved.The instantaneous dose rate reaches up to 10^(9)Gy/s,holding the potential for future FLASH radiotherapy research.
