Exploring a new and robust material for proton conduction is of significant importance to the scientific interest and technological importance.Polyoxometalates(POMs)are a class of molecular anion metal oxide clusters ...Exploring a new and robust material for proton conduction is of significant importance to the scientific interest and technological importance.Polyoxometalates(POMs)are a class of molecular anion metal oxide clusters with well-defined structures and diverse properties.Therefore,the design and synthesis of a POM-based material for proton conduction is extremely vital.Herein,a dimeric four tartaric acid-bridged tetra-Zr-incorporated arsenotungstate.展开更多
Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)...Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)(H_(2)O)_(21){Ca(H_(2)O)_(2)@Sb_(12)O_(18)[Ni_(2)(OH)(A-α-Si W_(10)O_(37))]_(3)}_(2)·40H_(2)O(1),was constructed using Keggintype polyoxotungstate A-α-Si W_(10)O_(37),along with Ni and Sb elements.The structure features a Tdsymmetric Sb_(12)O_(18)({Sb_(12)})cage that encapsulates an 8-coordinate Ca^(2+)ion at its face.Additionally,the{Sb_(12)}cage forms an 18-nuclear 3d-5p heterometallic cluster by connecting with three di-nuclear nickel clusters through shared oxygen atoms.Electrochemical impedance spectra studies reveal that the single crystal of 1 achieves a proton conductivity of 1.11×10^(-1)S/cm along the[110]direction and 1.04×10^(-1)S/cm along the[100]direction at 85℃ and 98%relative humidity(RH).Furthermore,the powder form of 1 exhibits a proton conductivity of 3.00×10^(-2)S/cm.These findings suggest that compound 1 holds promise as a practical proton conducting material.展开更多
Lanthanide metal-organic frameworks(Ln-MOFs)are widely used for fluorescence detection of ions and organic small molecules due to their excellent fluorescence properties.An aqueous stable europiumbased metal-organic f...Lanthanide metal-organic frameworks(Ln-MOFs)are widely used for fluorescence detection of ions and organic small molecules due to their excellent fluorescence properties.An aqueous stable europiumbased metal-organic framework,{I(CH_(3))_(2)NH_(2)]_(2)[Eu(TTDI)H_(2)O]_(2)·2H_(2)O·7DMF}_(n)(Eu-MOF,TTDI=5,5'-(thieno[3,2-b]-2,5-diphenyl)terephthalic)was synthesized and characterized,which demonstrates high selectivity and sensitivity fluorescence sensing of uric acid(UA)with a detection limit of 0.062μmol/L.Moreover,it also exhibits good proton conductivity with a maximum value of 3.34×10^(-3)S/cm at 55℃ under 98% relative humidity owing to its abundant hydrogen-bonding network.Therefore,this Eu-MOF is a potentially important multifunctional bioassay material.展开更多
To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis,two new lanthanum phosphite-oxalates with 3D...To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis,two new lanthanum phosphite-oxalates with 3D frameworks,designated as[La(HPO_(3))(C_(2)O_(4))0.5(H_(2)O)_(2)](La‑1)and(C_(6)H_(16)N_(2))(H_(3)O)[La_(2)(H_(2)PO_(3))_(3)(C_(2)O_(4))_(3)(H_(2)O)](La‑2)(C_(6)H_(14)N_(2)=cis-2,6-dimethylpiperazine),were prepared by hydrothermal and solvothermal conduction,respectively.La‑1 was constructed with lanthanum phosphite 2D layers and C_(2)O_(4)^(2-)groups,whereas La‑2 was constructed with lanthanum oxalate 2D layers and H_(2)PO^(3-)groups.Alternating current(AC)impedance spectra indicate that the pro-ton conductivities of both compounds could reach 10^(-4)S·cm^(-1)and remain highly durable at 75℃and 98%of rela-tive humidity(RH).Due to the abundance of H-bonds in La‑2,theσof La‑2 was higher than that of La‑1.La‑1 exhibited excellent water and pH stability.CCDC:2439965,La‑1;443776,La‑2.展开更多
Highly reduced molybdenum red(MR)clusters have emerged as a new type of polyoxomolybdates(POMos)and showed great potential as electron/proton reservoirs for energy conversion and storage,as well as for catalysis.Howev...Highly reduced molybdenum red(MR)clusters have emerged as a new type of polyoxomolybdates(POMos)and showed great potential as electron/proton reservoirs for energy conversion and storage,as well as for catalysis.However,the limited structural diversity of MR clusters significantly hinders further exploration of their potential as functional materials.Herein,we describe the synthesis of a novel highly reduced MR cluster{Mo_(49)}(compound 1)based on rational assembly of a variety of basic building blocks(BBs).In addition to the well-established BBs found in the family of MR clusters,the unique tetrahedral{MoVI 4}BB plays a key role in directing the assembly to afford trigonal pyramid-like structure of compound 1,which consists of 49 Mo and 148 O atoms with a high reduction degree of 73%.Moreover,at 80℃and 98%relative humidity(RH),the pellet sample of compound 1 displays good proton conductivity of 7.88×10^(-3)S/cm owing to the efficient hydrogen-bonded network built from the surface oxygen atoms,protons and vip water molecules.This research offers new insights into the assembly and synthesis of MR clusters through a BB strategy and manifests their significant potential for advanced applications.展开更多
The development of core-shell nanoclusters with controllable composition is of utmost importance as the material properties depend on their constituent elements.However,precisely tuning their compositions at the atomi...The development of core-shell nanoclusters with controllable composition is of utmost importance as the material properties depend on their constituent elements.However,precisely tuning their compositions at the atomic scale is not easily achieved because of the difficulty of using limited macroscopic synthetic methods for atomic-level modulation.In this work,we report an interesting example of precisely regulating the core composition of an inorganic core-shell-type cobalt polyoxoniobate[Co_(26)Nb_(36)O_(140)]^(32−)by controlling reaction conditions,in which the inner Co-core composition could be tune while retaining the outer Nb-shell composition of resulting product,leading to a series of isostructural species with a general formula of{Co_(26-n)Nb_(36+n)O_(140)}(n=0–2).These rare species not only can display good powder and single-crystal proton conductivities,but also might provide helpful and atomic-level insights into the syntheses,structures and composition modifications of inorganic amorphous core-shell heterometal oxide nanoparticles.展开更多
Metal-organic frameworks(MOFs)with inherent porosity and suspended acidic groups are promising proton conducting materials in water or aqua-ammonia media.Herein we report a new lanthanide phosphonate,namely,Dy_(2)(amp...Metal-organic frameworks(MOFs)with inherent porosity and suspended acidic groups are promising proton conducting materials in water or aqua-ammonia media.Herein we report a new lanthanide phosphonate,namely,Dy_(2)(amp_(2)H_(2))_(2)(mal)(H_(2)O)_(2)·5H2O(MDAF-6).It possesses a 3D open-framework structure,and shows a high NH_(3)adsorption capacity of 142.4 cm^(3)/g at P/P0=0.98 at 298 K due to acid-base interaction.Interestingly,the proton conductivity of MDAF-6-NH3 is enhanced by five orders of magnitude compared to MDAF-6 after 8.5 h exposure in saturated NH_(3)-H_(2)O vapor,indicating the importance of coexistent conjugate acid-base pairs of H_(3)O+-H_(2)O and NH_(4)^(+)-NH_(3)in promoting proton conduction.Magnetic studies of MDAF-6 revealed slow magnetization relaxation under zero dc field,characteristic of singlemolecule magnet behavior.This work provides not only a new multifunctional MOF material,but also a new strategy to improve proton conduction in aqua-ammonia medium.展开更多
To attain the objectives of carbon peaking and carbon neutrality,the development of stable and highperformance ion-conducting materials holds enormous relevance in various energy storage and conversion devices.Particu...To attain the objectives of carbon peaking and carbon neutrality,the development of stable and highperformance ion-conducting materials holds enormous relevance in various energy storage and conversion devices.Particularly,crystalline porous materials possessing built-in ordered nanochannels exhibit remarkable superiority in comprehending the ion transfer mechanisms with precision.In this regard,covalent organic frameworks(COFs)are highly regarded as a promising alternative due to their preeminent structural tunability,accessible well-defined pores,and excellent thermal/chemical stability under hydrous/anhydrous conditions.By the availability of organic units and the diversity of topologies and connections,advances in COFs have been increasing rapidly over the last decade and they have emerged as a new field of proton-conducting materials.Therefore,a comprehensive summary and discussion are urgently needed to provide an"at a glance"understanding of the prospects and challenges in the development of proton-conducting COFs.In this review,we target a comprehensive review of COFs in the field of proton conductivity from the aspects of design strategies,the proton conducting mechanism/features,the relationships of structure-function,and the application of research.The relevant content of theoretical simulation,advanced structural characterizations,prospects,and challenges are also presented elaborately and critically.More importantly,we sincerely hope that this progress report will form a consistent view of this field and provide inspiration for future research.展开更多
Through the mechanochemical method,sulfamic acid(SA)is successfully introduced into UiO-66-NH_(2)to form SA@UiO-66-NH_(2).In SA@UiO-66-NH_(2),the acidic cationic sulfiliminium(—S=NH_(2)^(+))moiety formed by the bridg...Through the mechanochemical method,sulfamic acid(SA)is successfully introduced into UiO-66-NH_(2)to form SA@UiO-66-NH_(2).In SA@UiO-66-NH_(2),the acidic cationic sulfiliminium(—S=NH_(2)^(+))moiety formed by the bridging bidentate binding mode between SA and the zirconium metal center can release protons,and SA actively participates in the construction of hydrogen-bonded network,thereby accelerating the proton conduction.At 95%RH(relative humidity)and 358 K,the proton conductivity of SA@UiO-66-NH_(2)can reach 1.42×10^(-2)S·cm^(-1),which is four orders of magnitude higher than that of the parent framework UiO-66-NH_(2).Meanwhile,this high proton conductivity can be maintained for at least 90 h.展开更多
A new coordination compound [Mg（L）（H2 O）5·H2 O]（NKU-109, H2 L=5-（4 H-1,2,4-triazol-4-yl）benzene-1,3-dicarboxylic acid） was solvothermally synthesized, featuring a supramolecular hydrogen-bonding network. ...A new coordination compound [Mg（L）（H2 O）5·H2 O]（NKU-109, H2 L=5-（4 H-1,2,4-triazol-4-yl）benzene-1,3-dicarboxylic acid） was solvothermally synthesized, featuring a supramolecular hydrogen-bonding network. A good proton conductivity of 5.87×10^-4S/cm was recorded at 70℃ and a relative humidity of75% in alternating current（AC） impedance experiment, which sheds a new light on the design of proton conduction materials based on coordination compounds.展开更多
Rapid dynamics and remarkable proton conduction induced by confined water in nanospaces have attracted much attentions from researchers,which is crucial for advancing the development of innovative proton conductors an...Rapid dynamics and remarkable proton conduction induced by confined water in nanospaces have attracted much attentions from researchers,which is crucial for advancing the development of innovative proton conductors and deepening comprehension of proton and water transport mechanisms within biological systems.In this aspect,carbon nanotubes(CNTs)are frequently employed as a research platform.However,they possess certain limitations,such as their inherent electronic conductivity and extreme hydrophobicity,which can impede the accurate assessment and precise regulation of proton conduction.We herein prepared two 2D COFs with different hydrophilic fragment,and obtained maximum acid-free proton conductivity of 3.04×10^(–4) S·cm^(–1) at 70℃ and 100%RH with Grotthuss type activation energy of 0.14 eV.This is mainly due to that the water molecules in the center of channel form strong hydrogen bonds,enhancing proton dissociation and guiding fast directional diffusion.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
Design of catalyst layers(CLs)with high proton conductivity in membrane electrode assemblies(MEAs)is an important issue for proton exchange membrane fuel cells(PEMFCs).Herein,an ultrathin catalyst layer was constructe...Design of catalyst layers(CLs)with high proton conductivity in membrane electrode assemblies(MEAs)is an important issue for proton exchange membrane fuel cells(PEMFCs).Herein,an ultrathin catalyst layer was constructed based on Pt-decorated nanoporous gold(NPG-Pt)with sub-Debye-length thickness for proton transfer.In the absence of ionomer incorporation in the CLs,these integrated carbon-free electrodes can deliver maximum mass-specific power density of 198.21 and 25.91 kW·gPt^(-1) when serving individually as the anode and cathode,at a Pt loading of 5.6 and 22.0 pg·cm^(-2),respectively,comparable to the best reported nano-catalysts for PEMFCs.In-depth quantitative experimental measurements and finite-element analyses indicate that improved proton conduction plays a critical role in activation,ohmic and mass transfer polarizations.展开更多
The key challenge for the use of polymer electrolytes is to realize a high ionic conductivity without scarifying their mechanical performance.Herein,we report a facile strategy to prepare a nanostructured polymer elec...The key challenge for the use of polymer electrolytes is to realize a high ionic conductivity without scarifying their mechanical performance.Herein,we report a facile strategy to prepare a nanostructured polymer electrolyte with both high proton conductivity and high modulus,based on the electrostatic self-assembly of polyoxometalate cluster H_(3)PW_(12)O_(40)(PW)and comb copolymer poly(ether-etherketone)-grafted-poly(vinyl pyrrolidone)(PEEK-gPVP).The incorporation of protonic acid PW can enable the PEEK-g-PVP to be highly proton conductive and create flexible composite electrolyte membranes.Moreover,nanoscale phase separation between PEEK domains and PVP/PW domains spontaneously occurs in these membranes,forming a bicontinuous structure with three-dimensional(3D)-connected PW networks.Due to the dual role of PW networks as both proton transport pathways and mechanical enhancers,these membranes exhibit proton conductivities higher than 30 mS cm^(−1) and modulus over 4 GPa.Notably,the direct methanol fuel cells equipped with these membranes show good cell performance.Given the wide tunability of comb copolymers and polyoxometalates,this system can be extended to develop a variety of functional electrolyte materials,for example,the lithium-ion conductive electrolytes by using polyoxometalatebased lithium salts,which provides a promising platform to explore versatile electrolyte materials for energy and electronic applications.展开更多
Two-dimensional covalent organic frameworks(2D COFs)have sparkled wide-ranging research to explore proton-conducting materials.However,the powder-pressed pellets or continuous membranes of 2D COFs are composed of rand...Two-dimensional covalent organic frameworks(2D COFs)have sparkled wide-ranging research to explore proton-conducting materials.However,the powder-pressed pellets or continuous membranes of 2D COFs are composed of randomly arranged crystallites,which are undesirable for proton transport via a shortcut pathway.We report a controlled strategy for preparing a conformably oriented free-standing COF membrane to address the critical challenge.A monofunctional aldehyde precursor is used as a modulator to enhance reversible association and optimize growth orientation in an interfacial polymerization system.The preferred face-on alignment is achieved throughout the membrane from its flat side to the nanoflake-standing side and,in turn,generates the unidirectional pore channels for accommodating 1,2,4-triazole as proton carriers.The composite merges distinctive features including orientation,crystallinity,porosity,and mechanical strength into one system,exhibiting ultrafast and stable anhydrous proton conduction at high operating temperatures with low activation energy.Our findings offer an innovative strategy for the oriented crystallization of free-standing COF membranes for energy conversion applications.展开更多
It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)throug...It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)through expanding the dimensionality of proton conduction.Three COF-based composites,COF-1@PA,COF-2@PA,and COF-3@PA(PA:phosphoric acid),are prepared by PA doping of three COFs with similar pore sizes but different amounts of hydrophilic groups.With the increase of hydrophilic groups,COFs can load more PA because of the enhanced hydrogen–bonding interactions between PA and the frameworks.powder X-ray diffraction(PXRD),scanning electron microscopy(SEM),and two-dimensional(2D)solid-state nuclear magnetic resonance(NMR)analyses show that PA can not only enter the channels of COF-3,but also insert into its 2D interlayers.This expands the proton conduction pathways from one-dimensional(1D)to three-dimensional(3D),which greatly improves the proton conductivity of COF-3.Meanwhile,the confinement effect of 1D channels and 2D layers of COF-3 also makes the hydrogen-bonded networks more orderly in COF-3@PA-30(30μL of PA loaded on COF-3).At 150℃,COF-3@PA-30 exhibits an ultrahigh anhydrous proton conductivity of 1.4 S·cm−1,which is a record of anhydrous proton conductivity reported to date.This work develops a new strategy for increasing the proton conductivity of 2D COF materials.展开更多
By using Co(NH3)63+as the template,a new complex HNU-38 was synthesized under hydrothermal reaction through the adoption of H3BTC and Cl-as the ligands(H3BTC=1,3,5-benzenetricarboxylic acid).HNU-38 crystallized in the...By using Co(NH3)63+as the template,a new complex HNU-38 was synthesized under hydrothermal reaction through the adoption of H3BTC and Cl-as the ligands(H3BTC=1,3,5-benzenetricarboxylic acid).HNU-38 crystallized in the monoclinic system,P21/c space group with a=9.9696(3),b=17.0580(6),c=16.5263(6)?,β=100.400(2)o,Z=4,V=2764.31(16)?3,Mr=883.63,Dc=2.123 g/cm3,F(000)=1736,S=0.920,R=0.0358 and wR=0.0838(Ⅰ>2σ(Ⅰ)).In HNU-38,the Cd2+and BTC3-were linked together to form layers with Cl-serving as the pillar.It should be noted that(H2O)n chains were found in the channels and play a co-templating role along with the Co(NH3)63+cations in HNU-38,and the proton conduction properties were investigated.展开更多
Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduction,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based hi...Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduction,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based high conducting materials.Herein we report the synthesis of sulfonate-functionalized polyoxovanadate-based MOPs for enhanced proton conduction via the synergistic effect from linker and metal cluster node.MOPs 1 and 2 exhibit octahedral cage configuration constructed from{V_(5)O_(9)Cl}vertex and 5-sulfoisophthalate linker.Owing to the ordered packing of octahedral cages along three axes,3D interpenetrated open channels that are lined with high-density sulfonates are thus formed within 2.Coupled with the proton-conductive{V_(5)O_(9)Cl}vertexs as well as protonated counterions,an extensive H-bonded network is therefore generated for facile proton transfer.2 exhibits high proton conductivity of 3.02×10^(-2)S cm^(-1)at 65℃under 90%RH,recording the highest value for MOPs pellet sample.This value is enhanced~1order of magnitude compared with that of carboxylate-functionalized analogue 3,clearly illustrating the advantage of combining linker and metal cluster node for enhanced proton conduction.This work will further promote the exploitation of high proton conductive MOPs-based materials by the synergy design strategy.展开更多
Proton-conducting materials have attracted considerable interest because of their extensive application in energy storage and conversion devices.Among them,metal-organic frameworks(MOFs)present tremendous development ...Proton-conducting materials have attracted considerable interest because of their extensive application in energy storage and conversion devices.Among them,metal-organic frameworks(MOFs)present tremendous development potential and possibilities for constructing novel advanced proton conductors due to their special advantages in crystallinity,designability,and porosity.In particular,several special design strategies for the structure of MOFs have opened new doors for the advancement of MOF proton conductors,such as charged network construction,ligand functionalization,metal-center manipulation,defective engineering,vip molecule incorporation,and pore-space manipulation.With the implementation of these strategies,proton-conducting MOFs have developed significantly and profoundly within the last decade.Therefore,in this review,we critically discuss and analyze the fundamental principles,design strategies,and implementation methods targeted at improving the proton conductivity of MOFs through representative examples.Besides,the structural features,the proton conduction mechanism and the behavior of MOFs are discussed thoroughly and meticulously.Future endeavors are also proposed to address the challenges of proton-conducting MOFs in practical research.We sincerely expect that this review will bring guidance and inspiration for the design of proton-conducting MOFs and further motivate the research enthusiasm for novel proton-conducting materials.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
基金supported by the National Natural Science Foundation of China(Nos.22071043 and 22203027)Shanxi Province Science Foundation(No.202303021211194)the program for the(Reserved)Discipline Leaders of Taiyuan Institute of Technology.
文摘Exploring a new and robust material for proton conduction is of significant importance to the scientific interest and technological importance.Polyoxometalates(POMs)are a class of molecular anion metal oxide clusters with well-defined structures and diverse properties.Therefore,the design and synthesis of a POM-based material for proton conduction is extremely vital.Herein,a dimeric four tartaric acid-bridged tetra-Zr-incorporated arsenotungstate.
基金the financial support from the National Natural Science Foundation of China(Nos.22109164 and 22371046)the Key Program of the Natural Science Foundation of Fujian Province(No.2021J02007)。
文摘Exploring the synthesis of novel structures is crucial for the development of functional materials.In this context,a novel and intriguing 3d-5p heterometallic cluster-substituted polyoxotungstate material,H_(29)Na_(9)(H_(2)O)_(21){Ca(H_(2)O)_(2)@Sb_(12)O_(18)[Ni_(2)(OH)(A-α-Si W_(10)O_(37))]_(3)}_(2)·40H_(2)O(1),was constructed using Keggintype polyoxotungstate A-α-Si W_(10)O_(37),along with Ni and Sb elements.The structure features a Tdsymmetric Sb_(12)O_(18)({Sb_(12)})cage that encapsulates an 8-coordinate Ca^(2+)ion at its face.Additionally,the{Sb_(12)}cage forms an 18-nuclear 3d-5p heterometallic cluster by connecting with three di-nuclear nickel clusters through shared oxygen atoms.Electrochemical impedance spectra studies reveal that the single crystal of 1 achieves a proton conductivity of 1.11×10^(-1)S/cm along the[110]direction and 1.04×10^(-1)S/cm along the[100]direction at 85℃ and 98%relative humidity(RH).Furthermore,the powder form of 1 exhibits a proton conductivity of 3.00×10^(-2)S/cm.These findings suggest that compound 1 holds promise as a practical proton conducting material.
基金Project supported by the National Natural Science Foundation of China(22365018)Jiangxi Provincial Key Laboratory of Functional Crystalline Materials Chemistry(2024SSY05161)Scientific Research Foundation of Jiangxi Provincial Education Department(GJJ210808)。
文摘Lanthanide metal-organic frameworks(Ln-MOFs)are widely used for fluorescence detection of ions and organic small molecules due to their excellent fluorescence properties.An aqueous stable europiumbased metal-organic framework,{I(CH_(3))_(2)NH_(2)]_(2)[Eu(TTDI)H_(2)O]_(2)·2H_(2)O·7DMF}_(n)(Eu-MOF,TTDI=5,5'-(thieno[3,2-b]-2,5-diphenyl)terephthalic)was synthesized and characterized,which demonstrates high selectivity and sensitivity fluorescence sensing of uric acid(UA)with a detection limit of 0.062μmol/L.Moreover,it also exhibits good proton conductivity with a maximum value of 3.34×10^(-3)S/cm at 55℃ under 98% relative humidity owing to its abundant hydrogen-bonding network.Therefore,this Eu-MOF is a potentially important multifunctional bioassay material.
文摘To develop proton-conducting materials with high hydrothermal and acid-base stability and to elucidate the proton-transport mechanism through visualized structural analysis,two new lanthanum phosphite-oxalates with 3D frameworks,designated as[La(HPO_(3))(C_(2)O_(4))0.5(H_(2)O)_(2)](La‑1)and(C_(6)H_(16)N_(2))(H_(3)O)[La_(2)(H_(2)PO_(3))_(3)(C_(2)O_(4))_(3)(H_(2)O)](La‑2)(C_(6)H_(14)N_(2)=cis-2,6-dimethylpiperazine),were prepared by hydrothermal and solvothermal conduction,respectively.La‑1 was constructed with lanthanum phosphite 2D layers and C_(2)O_(4)^(2-)groups,whereas La‑2 was constructed with lanthanum oxalate 2D layers and H_(2)PO^(3-)groups.Alternating current(AC)impedance spectra indicate that the pro-ton conductivities of both compounds could reach 10^(-4)S·cm^(-1)and remain highly durable at 75℃and 98%of rela-tive humidity(RH).Due to the abundance of H-bonds in La‑2,theσof La‑2 was higher than that of La‑1.La‑1 exhibited excellent water and pH stability.CCDC:2439965,La‑1;443776,La‑2.
基金National Natural Science Foundation of China(Nos.92161111 and 21901038)Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning,ChinaInternational Cooperation Fund of Science and Technology Commission of Shanghai Municipality,China(No.21130750100)。
文摘Highly reduced molybdenum red(MR)clusters have emerged as a new type of polyoxomolybdates(POMos)and showed great potential as electron/proton reservoirs for energy conversion and storage,as well as for catalysis.However,the limited structural diversity of MR clusters significantly hinders further exploration of their potential as functional materials.Herein,we describe the synthesis of a novel highly reduced MR cluster{Mo_(49)}(compound 1)based on rational assembly of a variety of basic building blocks(BBs).In addition to the well-established BBs found in the family of MR clusters,the unique tetrahedral{MoVI 4}BB plays a key role in directing the assembly to afford trigonal pyramid-like structure of compound 1,which consists of 49 Mo and 148 O atoms with a high reduction degree of 73%.Moreover,at 80℃and 98%relative humidity(RH),the pellet sample of compound 1 displays good proton conductivity of 7.88×10^(-3)S/cm owing to the efficient hydrogen-bonded network built from the surface oxygen atoms,protons and vip water molecules.This research offers new insights into the assembly and synthesis of MR clusters through a BB strategy and manifests their significant potential for advanced applications.
基金the financial support from the National Natural Science Foundation of China(Nos.21971039 and 22171045)and the Key Program of Natural Science Foundation of Fujian Province(No.2021J02007).
文摘The development of core-shell nanoclusters with controllable composition is of utmost importance as the material properties depend on their constituent elements.However,precisely tuning their compositions at the atomic scale is not easily achieved because of the difficulty of using limited macroscopic synthetic methods for atomic-level modulation.In this work,we report an interesting example of precisely regulating the core composition of an inorganic core-shell-type cobalt polyoxoniobate[Co_(26)Nb_(36)O_(140)]^(32−)by controlling reaction conditions,in which the inner Co-core composition could be tune while retaining the outer Nb-shell composition of resulting product,leading to a series of isostructural species with a general formula of{Co_(26-n)Nb_(36+n)O_(140)}(n=0–2).These rare species not only can display good powder and single-crystal proton conductivities,but also might provide helpful and atomic-level insights into the syntheses,structures and composition modifications of inorganic amorphous core-shell heterometal oxide nanoparticles.
基金the National Natural Science Foundation of China(No.21731003).
文摘Metal-organic frameworks(MOFs)with inherent porosity and suspended acidic groups are promising proton conducting materials in water or aqua-ammonia media.Herein we report a new lanthanide phosphonate,namely,Dy_(2)(amp_(2)H_(2))_(2)(mal)(H_(2)O)_(2)·5H2O(MDAF-6).It possesses a 3D open-framework structure,and shows a high NH_(3)adsorption capacity of 142.4 cm^(3)/g at P/P0=0.98 at 298 K due to acid-base interaction.Interestingly,the proton conductivity of MDAF-6-NH3 is enhanced by five orders of magnitude compared to MDAF-6 after 8.5 h exposure in saturated NH_(3)-H_(2)O vapor,indicating the importance of coexistent conjugate acid-base pairs of H_(3)O+-H_(2)O and NH_(4)^(+)-NH_(3)in promoting proton conduction.Magnetic studies of MDAF-6 revealed slow magnetization relaxation under zero dc field,characteristic of singlemolecule magnet behavior.This work provides not only a new multifunctional MOF material,but also a new strategy to improve proton conduction in aqua-ammonia medium.
基金financial support from the National Natural Science Foundation of China(21978024)the Beijing Natural Science Foundation(2202034)。
文摘To attain the objectives of carbon peaking and carbon neutrality,the development of stable and highperformance ion-conducting materials holds enormous relevance in various energy storage and conversion devices.Particularly,crystalline porous materials possessing built-in ordered nanochannels exhibit remarkable superiority in comprehending the ion transfer mechanisms with precision.In this regard,covalent organic frameworks(COFs)are highly regarded as a promising alternative due to their preeminent structural tunability,accessible well-defined pores,and excellent thermal/chemical stability under hydrous/anhydrous conditions.By the availability of organic units and the diversity of topologies and connections,advances in COFs have been increasing rapidly over the last decade and they have emerged as a new field of proton-conducting materials.Therefore,a comprehensive summary and discussion are urgently needed to provide an"at a glance"understanding of the prospects and challenges in the development of proton-conducting COFs.In this review,we target a comprehensive review of COFs in the field of proton conductivity from the aspects of design strategies,the proton conducting mechanism/features,the relationships of structure-function,and the application of research.The relevant content of theoretical simulation,advanced structural characterizations,prospects,and challenges are also presented elaborately and critically.More importantly,we sincerely hope that this progress report will form a consistent view of this field and provide inspiration for future research.
基金supported by the National Natural Science Foundation of China(22071019 and 21872021)the Basic Scientific Research Project of Liaoning Provincial Department of Education(LJKMZ20220968)
文摘Through the mechanochemical method,sulfamic acid(SA)is successfully introduced into UiO-66-NH_(2)to form SA@UiO-66-NH_(2).In SA@UiO-66-NH_(2),the acidic cationic sulfiliminium(—S=NH_(2)^(+))moiety formed by the bridging bidentate binding mode between SA and the zirconium metal center can release protons,and SA actively participates in the construction of hydrogen-bonded network,thereby accelerating the proton conduction.At 95%RH(relative humidity)and 358 K,the proton conductivity of SA@UiO-66-NH_(2)can reach 1.42×10^(-2)S·cm^(-1),which is four orders of magnitude higher than that of the parent framework UiO-66-NH_(2).Meanwhile,this high proton conductivity can be maintained for at least 90 h.
基金supported by the 973 Program of China (No. 2014CB845600)the National Natural Science Foundation of China (Nos. 21421001 and 21531005)the Natural Science Foundation of Tianjin(No. 15JCZDJC38800)
文摘A new coordination compound [Mg（L）（H2 O）5·H2 O]（NKU-109, H2 L=5-（4 H-1,2,4-triazol-4-yl）benzene-1,3-dicarboxylic acid） was solvothermally synthesized, featuring a supramolecular hydrogen-bonding network. A good proton conductivity of 5.87×10^-4S/cm was recorded at 70℃ and a relative humidity of75% in alternating current（AC） impedance experiment, which sheds a new light on the design of proton conduction materials based on coordination compounds.
基金supported by National Natural Science Foundation of China(52207238)China Postdoctoral Science Foundation(2023M731361)Jiangsu University Senior Talent Launch Fund.
文摘Rapid dynamics and remarkable proton conduction induced by confined water in nanospaces have attracted much attentions from researchers,which is crucial for advancing the development of innovative proton conductors and deepening comprehension of proton and water transport mechanisms within biological systems.In this aspect,carbon nanotubes(CNTs)are frequently employed as a research platform.However,they possess certain limitations,such as their inherent electronic conductivity and extreme hydrophobicity,which can impede the accurate assessment and precise regulation of proton conduction.We herein prepared two 2D COFs with different hydrophilic fragment,and obtained maximum acid-free proton conductivity of 3.04×10^(–4) S·cm^(–1) at 70℃ and 100%RH with Grotthuss type activation energy of 0.14 eV.This is mainly due to that the water molecules in the center of channel form strong hydrogen bonds,enhancing proton dissociation and guiding fast directional diffusion.
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financially supported by the National Natural Science Foundation of China(52073214,21603161,51671145,51761165012 and U1804255)the National Science Fund for Distinguished Young Scholars(No.51825102)the Tianjin Municipal Major Project of New Materials(No.16ZXCLGX00120).
文摘Design of catalyst layers(CLs)with high proton conductivity in membrane electrode assemblies(MEAs)is an important issue for proton exchange membrane fuel cells(PEMFCs).Herein,an ultrathin catalyst layer was constructed based on Pt-decorated nanoporous gold(NPG-Pt)with sub-Debye-length thickness for proton transfer.In the absence of ionomer incorporation in the CLs,these integrated carbon-free electrodes can deliver maximum mass-specific power density of 198.21 and 25.91 kW·gPt^(-1) when serving individually as the anode and cathode,at a Pt loading of 5.6 and 22.0 pg·cm^(-2),respectively,comparable to the best reported nano-catalysts for PEMFCs.In-depth quantitative experimental measurements and finite-element analyses indicate that improved proton conduction plays a critical role in activation,ohmic and mass transfer polarizations.
基金The authors acknowledge financial support from the National Natural Science Foundation of China(no.22075097)the Program for JLU Science and Technology Innovative Research Team(no.2017TD-10)the Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences(2020-09).
文摘The key challenge for the use of polymer electrolytes is to realize a high ionic conductivity without scarifying their mechanical performance.Herein,we report a facile strategy to prepare a nanostructured polymer electrolyte with both high proton conductivity and high modulus,based on the electrostatic self-assembly of polyoxometalate cluster H_(3)PW_(12)O_(40)(PW)and comb copolymer poly(ether-etherketone)-grafted-poly(vinyl pyrrolidone)(PEEK-gPVP).The incorporation of protonic acid PW can enable the PEEK-g-PVP to be highly proton conductive and create flexible composite electrolyte membranes.Moreover,nanoscale phase separation between PEEK domains and PVP/PW domains spontaneously occurs in these membranes,forming a bicontinuous structure with three-dimensional(3D)-connected PW networks.Due to the dual role of PW networks as both proton transport pathways and mechanical enhancers,these membranes exhibit proton conductivities higher than 30 mS cm^(−1) and modulus over 4 GPa.Notably,the direct methanol fuel cells equipped with these membranes show good cell performance.Given the wide tunability of comb copolymers and polyoxometalates,this system can be extended to develop a variety of functional electrolyte materials,for example,the lithium-ion conductive electrolytes by using polyoxometalatebased lithium salts,which provides a promising platform to explore versatile electrolyte materials for energy and electronic applications.
基金supported by the National Natural Science Foundation of China (51973039,52173197,52131308)
文摘Two-dimensional covalent organic frameworks(2D COFs)have sparkled wide-ranging research to explore proton-conducting materials.However,the powder-pressed pellets or continuous membranes of 2D COFs are composed of randomly arranged crystallites,which are undesirable for proton transport via a shortcut pathway.We report a controlled strategy for preparing a conformably oriented free-standing COF membrane to address the critical challenge.A monofunctional aldehyde precursor is used as a modulator to enhance reversible association and optimize growth orientation in an interfacial polymerization system.The preferred face-on alignment is achieved throughout the membrane from its flat side to the nanoflake-standing side and,in turn,generates the unidirectional pore channels for accommodating 1,2,4-triazole as proton carriers.The composite merges distinctive features including orientation,crystallinity,porosity,and mechanical strength into one system,exhibiting ultrafast and stable anhydrous proton conduction at high operating temperatures with low activation energy.Our findings offer an innovative strategy for the oriented crystallization of free-standing COF membranes for energy conversion applications.
基金We are grateful for financial support from the National Natural Science Foundation of China(Nos.21771193 and 22275210)Key Research and Development Projects of Shandong Province(No.2019JZZY010331).
文摘It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)through expanding the dimensionality of proton conduction.Three COF-based composites,COF-1@PA,COF-2@PA,and COF-3@PA(PA:phosphoric acid),are prepared by PA doping of three COFs with similar pore sizes but different amounts of hydrophilic groups.With the increase of hydrophilic groups,COFs can load more PA because of the enhanced hydrogen–bonding interactions between PA and the frameworks.powder X-ray diffraction(PXRD),scanning electron microscopy(SEM),and two-dimensional(2D)solid-state nuclear magnetic resonance(NMR)analyses show that PA can not only enter the channels of COF-3,but also insert into its 2D interlayers.This expands the proton conduction pathways from one-dimensional(1D)to three-dimensional(3D),which greatly improves the proton conductivity of COF-3.Meanwhile,the confinement effect of 1D channels and 2D layers of COF-3 also makes the hydrogen-bonded networks more orderly in COF-3@PA-30(30μL of PA loaded on COF-3).At 150℃,COF-3@PA-30 exhibits an ultrahigh anhydrous proton conductivity of 1.4 S·cm−1,which is a record of anhydrous proton conductivity reported to date.This work develops a new strategy for increasing the proton conductivity of 2D COF materials.
基金supported by the National Natural Science Foundation of China(21761010)Natural Science Foundation of Hainan Province(217055 and 217018)+1 种基金the Hainan University start-up fund(kyqd1654 and KYQD(ZR)1806)the Opening Project of Key Laboratory of Polyoxometalate Science of Ministry of Education。
文摘By using Co(NH3)63+as the template,a new complex HNU-38 was synthesized under hydrothermal reaction through the adoption of H3BTC and Cl-as the ligands(H3BTC=1,3,5-benzenetricarboxylic acid).HNU-38 crystallized in the monoclinic system,P21/c space group with a=9.9696(3),b=17.0580(6),c=16.5263(6)?,β=100.400(2)o,Z=4,V=2764.31(16)?3,Mr=883.63,Dc=2.123 g/cm3,F(000)=1736,S=0.920,R=0.0358 and wR=0.0838(Ⅰ>2σ(Ⅰ)).In HNU-38,the Cd2+and BTC3-were linked together to form layers with Cl-serving as the pillar.It should be noted that(H2O)n chains were found in the channels and play a co-templating role along with the Co(NH3)63+cations in HNU-38,and the proton conduction properties were investigated.
基金supported by the National Natural Science Foundation of China(Nos.92161111,21901037,21901038,21871042)Shanghai Pujiang Program(No.19PJ1400200)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning and International Cooperation Fund of Science and Technology Commission of Shanghai Municipality(No.21130750100)。
文摘Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduction,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based high conducting materials.Herein we report the synthesis of sulfonate-functionalized polyoxovanadate-based MOPs for enhanced proton conduction via the synergistic effect from linker and metal cluster node.MOPs 1 and 2 exhibit octahedral cage configuration constructed from{V_(5)O_(9)Cl}vertex and 5-sulfoisophthalate linker.Owing to the ordered packing of octahedral cages along three axes,3D interpenetrated open channels that are lined with high-density sulfonates are thus formed within 2.Coupled with the proton-conductive{V_(5)O_(9)Cl}vertexs as well as protonated counterions,an extensive H-bonded network is therefore generated for facile proton transfer.2 exhibits high proton conductivity of 3.02×10^(-2)S cm^(-1)at 65℃under 90%RH,recording the highest value for MOPs pellet sample.This value is enhanced~1order of magnitude compared with that of carboxylate-functionalized analogue 3,clearly illustrating the advantage of combining linker and metal cluster node for enhanced proton conduction.This work will further promote the exploitation of high proton conductive MOPs-based materials by the synergy design strategy.
基金supported by the China Scholarship Council(No.202408120105)National Natural Science Foundation of China(32301530)+5 种基金Young Elite Scientist Sponsorship Program by CAST(No.YESS20230242)Tianjin Excellent Special Commissioner for Agricultural Science and Technology Project(23ZYCGSN00580)Natural Science Foundation of Tianjin(23JCZDJC00630)China Postdoctoral Science Foundation(2023M740563)State Key Laboratory of Pulp and Paper Engineering(202412,202413)the Central Publicinterest Scientific Institution Basa Research Fund(No.Y2022QC30).
文摘Proton-conducting materials have attracted considerable interest because of their extensive application in energy storage and conversion devices.Among them,metal-organic frameworks(MOFs)present tremendous development potential and possibilities for constructing novel advanced proton conductors due to their special advantages in crystallinity,designability,and porosity.In particular,several special design strategies for the structure of MOFs have opened new doors for the advancement of MOF proton conductors,such as charged network construction,ligand functionalization,metal-center manipulation,defective engineering,vip molecule incorporation,and pore-space manipulation.With the implementation of these strategies,proton-conducting MOFs have developed significantly and profoundly within the last decade.Therefore,in this review,we critically discuss and analyze the fundamental principles,design strategies,and implementation methods targeted at improving the proton conductivity of MOFs through representative examples.Besides,the structural features,the proton conduction mechanism and the behavior of MOFs are discussed thoroughly and meticulously.Future endeavors are also proposed to address the challenges of proton-conducting MOFs in practical research.We sincerely expect that this review will bring guidance and inspiration for the design of proton-conducting MOFs and further motivate the research enthusiasm for novel proton-conducting materials.
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.
