Metal-organic frameworks(MOFs)with high porosity,specific surface area,and unique topologies are highly regarded for their applications in photocatalysis,medical treatment,and environmental pollutant degradation.Howev...Metal-organic frameworks(MOFs)with high porosity,specific surface area,and unique topologies are highly regarded for their applications in photocatalysis,medical treatment,and environmental pollutant degradation.However,due to the limitations of the tumor microenvironment(TME),traditional MOFs have limited efficacy in this environment.This paper designs multi-metal oxide-based heterostructure POMOFs nanoreactors with a nesting doll-like structure.This new structure not only exhibits therapeutic effects in TME but also utilizes ultrasound(US)to enhance the release of reactive oxygen species(ROS)for CDT&SDT co-therapy,becoming an effective sound sensitizer for destroying tumor cells.In summary,our study proposes an idea for constructing multi-metal oxide-based heterostructure MOFs nanoreactors material with a nesting doll-like structure to enhance ROS release and synergistically treat tumor diseases.展开更多
The kinetics of alkaline hydrogen evolution reaction(HER)of platinum(Pt)is markedly slower owing to the poor proton supply rate and sluggish water dissociation.Herein,we report an efficient strategy based on polyoxome...The kinetics of alkaline hydrogen evolution reaction(HER)of platinum(Pt)is markedly slower owing to the poor proton supply rate and sluggish water dissociation.Herein,we report an efficient strategy based on polyoxometalates(POMs)hydrogels to prepare the selfsupporting porous conductive carbon aerogels embedded with Pt-doped molybdenum carbide(Pt@Mo_(2)C)active sites for promoting the alkaline HER performance.It is found that as-prepared self-supporting Pt@Mo_(2)C carbon aerogels possesses continuous porous conductive networks,which improves the electron and mass transfer.Moreover,the heterostructure of Pt and Mo2_(2)C can significantly promote the water dissociation with the assistant of Mo-OH and Pt-H bonding,thereby improving alkaline HER activities.The optimized Pt@Mo_(2)C/Carbon fiber paper(Pt@Mo_(2)C/CFP)electrocatalyst has Pt content as low as 0.03 mg cm^(-2),which can achieve overpotential of 17 mV at 10 mA cm^(-2),surpassing the commercial Pt/C.Moreover,it exhibits an excellent sustained stability for over 100 h at 500 mA cm^(-2)in a practical alkaline water electrolyzer.The work offers new opportunities to design and synthesize superior performance electrocatalysts for the alkaline HER.展开更多
Constructing clus ter heterostructures with strongly coupled interfaces is of great importance to accelerating the catalytic reactions that involve multiple intermediates.Herein,a strongly coupled cluster heterostruct...Constructing clus ter heterostructures with strongly coupled interfaces is of great importance to accelerating the catalytic reactions that involve multiple intermediates.Herein,a strongly coupled cluster heterostructure composed of platinum and molybdenum carbide(Pt@Mo_(2)C)derived from polyoxometalate clusters is designed to achieve excellent alkaline hydrogen evolution reaction.The Pt@Mo_(2)C cluster exhibits strong electronic interactions between Pt and Mo_(2)C,working together to facilitate the H_(2)O dissociation by concurrently binding intermediates(Pt-H*and Mo-OH*),thus accelerating the kinetics of the rate-determining Volmer step.Theoptimized Pt@Mo_(2)C exhibits a high mass activity of12.1 A·mgpt^(-1),19.2 times higher than that of 20%Pt/C in alkaline media.Moreover,it can be stabilized at a current density of 100 mA·cm^(-2)for more than 200 h.This work demonstrated the superiority of the cluster heterostructures and co-catalytic effect towards the development of highly efficient electrocatalysts.展开更多
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting.Nowadays,novel strategies of disease diagnosis and therapies are in blooming development as rema...Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting.Nowadays,novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development.Under the current requirements to high production capacity and novel synthesis methods of drugs,green synthesis based on strategies with different ways of empowering,advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging.Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes.Polyoxometalates(POMs)are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials,catalysis and medicine.In this review,the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts,alternative reaction equipment based novel synthesis protocols.The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.展开更多
For a long time,researchers have been fascinated by the structurally diverse and high-performance characteristics of polyoxometalates(POMs).Modifying POMs with various types and properties of metals has broadened thei...For a long time,researchers have been fascinated by the structurally diverse and high-performance characteristics of polyoxometalates(POMs).Modifying POMs with various types and properties of metals has broadened their applications in fields such as magnetism,luminescence,and catalysis.However,despite the discovery of numerous POM structures doped with transition metal ions,the development of aluminum(Al)as aⅢA group metal in the POM field has been slow.Aluminum,the most abundant metal in nature,offers innate electron-deficient properties that,when combined with highly charged POMs,could introduce novel structures and excellent functionalities like proton conduction to this field.Therefore,this review will address the gap in summarizing Al-containing POMs by categorizing and summarizing the synthesis,structural characteristics,and properties of Al-containing POMs,aiming to provide a theoretical foundation for exploring POM structures doped with Al atoms.The review also analyzes and forecasts the prospects in this field.展开更多
Polyoxometalates(POMs)are molecular metal-oxide clusters with precise chemical composition and architecture.Besides their bioactivities,electron-rich POMs have shown potential for enhancing synergistic therapy,such as...Polyoxometalates(POMs)are molecular metal-oxide clusters with precise chemical composition and architecture.Besides their bioactivities,electron-rich POMs have shown potential for enhancing synergistic therapy,such as photothermal therapy(PTT),photodynamic therapy(PDT),and chemo-dynamic therapy(CDT),through near-infrared region(NIR)absorption and redox reactions.展开更多
A series of novel photocatalysts, H3PW12O40-Y-TiO2 nanocomposites with different H3PW12O40 loading levels （10%-40%） were prepared by impregnation method. And the Y-TiO2 support, doped with yttrium, was synthesized v...A series of novel photocatalysts, H3PW12O40-Y-TiO2 nanocomposites with different H3PW12O40 loading levels （10%-40%） were prepared by impregnation method. And the Y-TiO2 support, doped with yttrium, was synthesized via sol-gel technique. The prepared catalysts were characterized by Fourier transform infrared spectroscopy （FT-IR）, powder X-ray diffraction （XRD）, nitrogen adsorption-desorption analysis and scanning electron microscopy （SEM）. The processes allowed obtaining Keggin structure and crystallized anatase with large BET surface area as well as uniform distribution. The effects of H3PW12O40 loadings, catalyst dose, initial pH and concentration of dye solution on the degradation kinetics of methyl orange under UV light （λ≥365 nm） were discussed. Kinetics studies showed that the photocatalytic degradation of methyl orange fitted the apparent first-order reaction. Methyl orange was totally degraded in 21 min under optimum conditions： 20% loading, 0.03 g dose and pH 1.0. The catalyst was stable and easily to be separated from reaction system for recovery.展开更多
A novel supported polyoxometalate （POM）, phosphotungstic acid immobilized into yttrium-doped TiO2 （HPW-Y-TiO2） nano photocatalyst was prepared via sol-gel and impregnation method. The samples were characterized us...A novel supported polyoxometalate （POM）, phosphotungstic acid immobilized into yttrium-doped TiO2 （HPW-Y-TiO2） nano photocatalyst was prepared via sol-gel and impregnation method. The samples were characterized using Fourier transform in- frared spectroscopy （FT-IR）, X-ray diffraction （XRD） and N2 absorption-desorption analysis. The results showed that the supported POM exhibited Keggin structure and anatase phase with large BET surface area. The influences of inorganic anions and organic addi- tives on the photocatalytic degradation of azo dye methyl orange with HPW-Y-TiO2 as photocatalyst under UV light （2〉365 urn） were investigated. Results showed that inorganic anions CI, 504^2-, CO32 and NO3 had inhibition effect on the degradation of methyl orange. A great enhancement of degradation rate was obtained while H202 and ethyl alcohol were applied. The degradation rates improved with the increase of H202 concentration. The optimum additive amount of ethyl alcohol was 0.5 mol/L. The possible mechanisms of the effects of additives on methyl orange degradation were discussed.展开更多
Heterogeneously catalyzed hydrolytic dehydrogenation of ammonia borane is a remarkable structure sensitive reaction. In this work, a strategy by using polyoxometalates(POMs) as the ligands is proposed to engineer the ...Heterogeneously catalyzed hydrolytic dehydrogenation of ammonia borane is a remarkable structure sensitive reaction. In this work, a strategy by using polyoxometalates(POMs) as the ligands is proposed to engineer the surface and electronic properties of Pt/CNT catalysts toward the enhanced hydrogen generation rate and durability. Three kinds of POMs, i.e., silicotungstic acid(STA), phosphotungstic acid(PTA)and molybdophosphoric acid(PMA), are comparatively studied, among which the STA shows positive effects on the catalytic activity and durability. A catalyst structure-performance relationship is established by a combination of kinetic and isotopic analyses with multiple characterization techniques, such as HAADF-STEM, EDS, Raman spectroscopy and XPS. It is shown that the STA compared to the other two POMs can increase the Pt binding energy and thus promote the reaction. The insights demonstrated here could open a new avenue for boosting the reaction by employing the POMs as the ligands to engineer the catalyst electronic properties.展开更多
Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for de...Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for developing a lignin catalytic decomposition process could be developed by exploring the transformation mechanisms of various model compounds. Herein, decomposition of a lignin model compound, 2-phenoxyacetophenone （2-PAP）, was investigated over several ce-sium-exchanged polyoxometalate （Cs-POM） catalysts. Decomposition of 2-PAP can follow two dif-ferent mechanisms： an active hydrogen transfer mechanism or an oxonium cation mechanism. The mechanism for most reactions depends on the competition between the acidity and redox proper-ties of the catalysts. The catalysts of POMs perform the following functions： promoting active hy-drogen liberated from ethanol and causing formation of and then temporarily stabilizing oxonium cations from 2-PAP. The use of Cs-PMo, which with strong redox ability, enhances hydrogen libera-tion and promotes liberated hydrogen transfer to the reaction intermediates. As a consequence, complete conversion of 2-PAP （〉99%） with excellent selectivities to the desired products （98.6% for phenol and 91.1% for acetophenone） can be achieved.展开更多
Bismuth‐based photocatalysts are a class of excellent visible‐light photocatalysts;however,their redox activity is relatively poor and the efficiency of photogenerated carrier separation is low,limiting their develo...Bismuth‐based photocatalysts are a class of excellent visible‐light photocatalysts;however,their redox activity is relatively poor and the efficiency of photogenerated carrier separation is low,limiting their development and application in the field of photocatalysis.To address these issues,a series of polyoxometalate PW_(12)O_(40)^(3–)‐doped Bi_(2)O_(3–x)/Bi Schottky photocatalysts PW_(12)@Bi_(2)O_(3–x)/Bi‐n(PBOB‐n,where n is the amount of NaBH4,i.e.,6,12,18,24,and 48 mg)were prepared by a simple electrospinning/calcination/in‐situ NaBH4 reduction method.In this composite photocatalyst,the doping of PW_(12) could effectively adjust the electronic structure of Bi_(2)O_(3–x) and improve its redox properties.As a shallow electron trap,PW_(12) promoted the separation of the photogenerated carriers.Furthermore,desirable Schottky junction between the metal Bi nanoparticles and PW_(12)@Bi_(2)O_(3–x) further accelerated the separation of the photogenerated carriers.The synergistic effect of the aforementioned factors endowed PBOB‐n with excellent photocatalytic activity.Among the samples,PBOB‐18 exhibited superior photocatalytic activity.Under visible‐light irradiation,93.7%(20 mg catalyst)of 20 ppm tetrabromobisphenol A(TBBPA,20 mL)was degraded in 60 min.Its activity was 4.4 times higher than that of Bi_(2)O_(3).PBOB‐18 also exhibited an ultrahigh photocatalytic performance for the removal of NO.Its removal rate(600 ppb)reached 83.3%in 30 min,making it one of the most active Bi‐based photocatalysts.Furthermore,the photocatalytic mechanisms of PBOB‐18 for TBBPA and NO have been proposed.This work provides a new direction and reference for the design of low‐cost,efficient,stable,and versatile photocatalysts.展开更多
A series of photocatalysts, K11[Ln(PW11O39)2]/PVA (Ln=La, Ce, Pr, Nd, Sm) were prepared by K11[Ln(PW11O39)2] (Ln=La, Ce, Pr, Nd, Sm) containing five kinds of lanthanides and polyvinyl alcohol as the support. The catal...A series of photocatalysts, K11[Ln(PW11O39)2]/PVA (Ln=La, Ce, Pr, Nd, Sm) were prepared by K11[Ln(PW11O39)2] (Ln=La, Ce, Pr, Nd, Sm) containing five kinds of lanthanides and polyvinyl alcohol as the support. The catalysts obtained were characterized by Fourier transform infrared spectra, UV-vis spectra, powder X-ray diffraction, and scanning electron microscopy, indicating that the structure of K11[Ln(PW11O39)2] and polyvinyl alcohol remained intact, respectively. The photocatalysts exhibited efficient catalytic activity to degrade methyl orange, Congo Red, Ponceau 2R. The maximal degradation conversions of the three kinds of dyes were 99.58%, 47.61%, 72.42%, respectively.展开更多
Three sandwich-like[Ln_(2)Fe_(2)(B-α-FeW_9O_(34))_(2)]^(10-) clusters(Ln_(2)Fe_(4),Ln=Dy(1),Ho(2),and Y(3)) were obtained by reacting Na_9[B-α-SbW_9O_(33)],Ln_(2)O_(3),FeCl_(3)·6H_(2)O and KH_(2)PO_(4).The[B-α...Three sandwich-like[Ln_(2)Fe_(2)(B-α-FeW_9O_(34))_(2)]^(10-) clusters(Ln_(2)Fe_(4),Ln=Dy(1),Ho(2),and Y(3)) were obtained by reacting Na_9[B-α-SbW_9O_(33)],Ln_(2)O_(3),FeCl_(3)·6H_(2)O and KH_(2)PO_(4).The[B-α-FeW_9O_(34)]^(11-) units were formed via the in situ conversion of lacunary polyoxometalates(POM)[B-α-SbW_9O_(33)]^(9-)and the Ln^(3+)ions were generated from the slow dissolution of Ln_(2)O_(3),both of which play important roles in the synthesis of Ln_(2)Fe_(4).Ln_(2)Fe_(4) is the first 3d-4f cluster assembled from d-metal heteroatom-containing POM.The Dy_(2)Fe_(4) cluster exhibits single-molecule magnet properties with an 80 K energy barrier in an optimal DC field.Cyclic voltammetry tests and controlled-potential coulometry experiments show that the polyoxometalate Fe heteroatom in clusters 1-3 is also electrochemically active.展开更多
Health care and medical care have always been dominant topics in human society.The field of precision medicine,iatrotechnics revolution and timely on-demand detection have continued to evolve in response to increasing...Health care and medical care have always been dominant topics in human society.The field of precision medicine,iatrotechnics revolution and timely on-demand detection have continued to evolve in response to increasing demands from the society.Furthermore,the emergence of innovative materials and their applications offer promising prospects for advancing global health.Polyoxometalates(POMs)are negatively-charged molecular metal oxides with well-defined structures,beautiful geometries and nanoscale sizes.Owing to their vast diversity in composition,structure,nuclearity and charge,they constitute a significant subcategory of inorganic clusters that contain bridging oxygen atoms between two or more metal ions.Nowadays,POMs based nanocomposites have been widely applied in the field of disease diagnosis,anticancer therapy and antibacterial therapy as new generation bioactive materials.In this review,the recent advances of POMs based nanocomposites in bioapplications are summarized and the future perspectives are discussed.展开更多
The visible-light-induced selective oxidation of ubiquitous C–H bonds into valuable C=O bonds under aerobic conditions is one of the most attractive approaches for the construction of carbonyl-containing molecules.In...The visible-light-induced selective oxidation of ubiquitous C–H bonds into valuable C=O bonds under aerobic conditions is one of the most attractive approaches for the construction of carbonyl-containing molecules.In this work,two transition metal-containing Nb/W mixed-addendum POMs dimers with the formula of K_(2)Na_(2)H_(5)[(Fe(H_(2)O)_(4))_(3)(P_(2)W_(15)Nb_(3)O_(62))_(2)]·24H_(2)O(POM[Fe])and K_(2)Na_(3)H_(4)[(Cr(H_(2)O)_(4))_(3)(P_(2)W_(15)Nb_(3)O_(62))_(2)]·32H_(2)O(POM[Cr])have been synthesized and characterized by various analytical and spectral techniques.POM[Fe]was proved to be an efficient photocatalyst for benzylic C–H oxidation under visible light and using oxygen as an oxidant to produce the corresponding carbonyl complex in good yields.A plausible mechanism involving superoxide radical was proposed for the catalytic reaction.POM[Fe]showed good reusability in the recycling experiments.IR spectroscopy and XRD analysis indicate that POM[Fe]can retain its integrity after catalysis.展开更多
Crystalline porous ionic salts(CPISs) represent a new type of porous materials constructed by electrostatic interaction, however, synthesis of CPISs bearing pre-designed functionality while exhibiting permanent porosi...Crystalline porous ionic salts(CPISs) represent a new type of porous materials constructed by electrostatic interaction, however, synthesis of CPISs bearing pre-designed functionality while exhibiting permanent porosity is still challenging. Herein we report the facile synthesis of a series of CPISs 1-3 built from photocatalytic-active polyoxometalate(POM) clusters and cationic Zr-based capsules, which showed open porous frameworks with BET surface area up to 33 m^(2)/g and high activity and selectivity for photodriven aerobic oxidation of alcohols to aldehydes. Compared with the pristine POM cluster {W10}, 1 can promote the reaction in much higher efficiency due to the concerted catalysis of preinstalled {W10} and Zr-based capsule together with open channels. This work highlights the advantage of CPISs as porous heterogeneous catalysts in organic transformation, and may shed light on the rational design of more delicate CPISs-derived functional materials.展开更多
Polyoxometalates(POMs)have conducive properties such as controlled Bronsted and Lewis acidity,high thermal stability,nontoxic nature,tunable solubility,and less corrosiveness.POMs have been extensively applied in cata...Polyoxometalates(POMs)have conducive properties such as controlled Bronsted and Lewis acidity,high thermal stability,nontoxic nature,tunable solubility,and less corrosiveness.POMs have been extensively applied in catalytic organic reactions and have an exciting prospect for industrial applications.This review summarized recent progress in the application of POMs as acid catalysts for various organic reactions including C-C bond formation,C-N bond formation,C-O bond formation,heterocyclic synthesis reactions,cyanosilylation and hydrolysis reactions.Various POMs catalysts including heteropoly acids(HPAs)and cationic functionalized HPAs with Bronsted acidity,HPAs supported on non-precious metal support with Bronsted acidity(or both Bronsted and Lewis acidity),transition metal substituted POMs with Lewis acidity were applied in above reactions.This review attempts to provide up-to-date information about POMs acid-catalyzed organic reactions and propose future prospects.展开更多
Hybrid self-assembled multilayer films were prepared by alternate adsorption of 1,10-diaminodecane (1,10-DAD) and Keggin polyoxometalates of SiW12O404-, SiW11VO405-, and PMo12O403-, respectively. The films were repro...Hybrid self-assembled multilayer films were prepared by alternate adsorption of 1,10-diaminodecane (1,10-DAD) and Keggin polyoxometalates of SiW12O404-, SiW11VO405-, and PMo12O403-, respectively. The films were reproducibly grown at each adsorption cycle as monitored by UV spectroscopy.展开更多
Solar vapor generation(SVC)represents a promising technique for seawater desalination to alleviate the global water crisis and energy shortage.One of its main bottleneck problems is that the evaporation efficiency and...Solar vapor generation(SVC)represents a promising technique for seawater desalination to alleviate the global water crisis and energy shortage.One of its main bottleneck problems is that the evaporation efficiency and stability are limited by salt crystallization under high-salinity brines.Herein,we demonstrate that the 3D porous melamine-foam(MF)wrapped by a type of self-assembling composite materials based on reduced polyoxometalates(i.e.heteropoly blue,HPB),oleic acid(OA),and polypyrrole(PPy)(labeled with MF@HPB-PPy_(n)-OA)can serve as efficient and stable SVC material at high salinity.Structural characterizations of MF@HPB-PPy_(n)-OA indicate that both hydrophilic region of HPBs and hydrophobic region of OA co-exist on the surface of composite materials,optimizing the hydrophilic and hydrophobic interfaces of the SVC materials,and fully exerting its functionality for ultrahigh water-evaporation and anti-salt fouling.The optimal MF@HPB-PPy_(10)-OA operates continuously and stably for over 100 h in 10wt%brine.Furthermore,MF@HPB-PPy_(10)-OA accomplishes complete salt-water separation of 10wt%brine with 3.3kgm^(-2)h^(-1)under 1-sun irradiation,yielding salt harvesting efficiency of 96.5%,which belongs to the record high of high-salinity systems reported so far and is close to achieving zero liquid discharge.Moreover,the low cost of MF@HPB-PPy_(10)-OA(2.56$m^(-2))suggests its potential application in the practical SVC technique.展开更多
Two new hybrid polyoxotungstates, [Co（2,2＇-bipy）3][a-H5PW11CoO40]-3H2O 1 and [Fe（2,2＇-bipy）3]2[a-HBW12O40]-2.5H2O 2 （2,2＇-bipy = 2,2＇-dipyridyl）, have been hydrothermally synthesized and characterized by IR,...Two new hybrid polyoxotungstates, [Co（2,2＇-bipy）3][a-H5PW11CoO40]-3H2O 1 and [Fe（2,2＇-bipy）3]2[a-HBW12O40]-2.5H2O 2 （2,2＇-bipy = 2,2＇-dipyridyl）, have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray structural analyses. The results of X-ray crystallography analyses exhibit that 1 consists of one a-Keggin anion [a-H5PW11CoO40]2- and one isolated [Co（2,2＇-bipy）3]2＋ complex, while 2 is constructed from one a-Keggin anion [a- HBW12O40]4- and two isolated [Fe（2,2＇-bipy）3]2＋ cations. The data for 1： orthorhombic system, space group Pbcn, a = 16.062（6）, b = 27.278（10）, c = 16.951（6）A, V = 7427（5）A3 and Z = 4; and those for 2： triclinic system, space group P1, a = 13.787（3）, b = 17.857（5）, c = 18.918（5）A, a = 88.009（12）, β = 72.768（10）, γ = 74.935（10）°, V = 4291（2）A3 and Z = 2.展开更多
基金funded by the National Natural Science Foundation of China(Nos.52372264,32271609and 52473109)+2 种基金The Natural Science Foundation of Heilongjiang Province of China(No.LH2023B002)The Fundamental Research Funds for the Central Universities(No.2572023CT12)Undergraduate Training Programs for Innovations by NEFU(No.202310225565)。
文摘Metal-organic frameworks(MOFs)with high porosity,specific surface area,and unique topologies are highly regarded for their applications in photocatalysis,medical treatment,and environmental pollutant degradation.However,due to the limitations of the tumor microenvironment(TME),traditional MOFs have limited efficacy in this environment.This paper designs multi-metal oxide-based heterostructure POMOFs nanoreactors with a nesting doll-like structure.This new structure not only exhibits therapeutic effects in TME but also utilizes ultrasound(US)to enhance the release of reactive oxygen species(ROS)for CDT&SDT co-therapy,becoming an effective sound sensitizer for destroying tumor cells.In summary,our study proposes an idea for constructing multi-metal oxide-based heterostructure MOFs nanoreactors material with a nesting doll-like structure to enhance ROS release and synergistically treat tumor diseases.
基金financially supported by the National Natural Science Foundation of China(Nos.52303274 and 22171287)the Natural Science Foundation of Shandong Province(Nos.ZR2022QE175 and ZR2024QB076)+2 种基金the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China(Nos.2023KJ280 and 2021KJ014)Taishan Scholar Project of Shandong Province(No.tsqn202103046)the Fundamental Research Funds for the Central Universities(No.24CX07007A)
文摘The kinetics of alkaline hydrogen evolution reaction(HER)of platinum(Pt)is markedly slower owing to the poor proton supply rate and sluggish water dissociation.Herein,we report an efficient strategy based on polyoxometalates(POMs)hydrogels to prepare the selfsupporting porous conductive carbon aerogels embedded with Pt-doped molybdenum carbide(Pt@Mo_(2)C)active sites for promoting the alkaline HER performance.It is found that as-prepared self-supporting Pt@Mo_(2)C carbon aerogels possesses continuous porous conductive networks,which improves the electron and mass transfer.Moreover,the heterostructure of Pt and Mo2_(2)C can significantly promote the water dissociation with the assistant of Mo-OH and Pt-H bonding,thereby improving alkaline HER activities.The optimized Pt@Mo_(2)C/Carbon fiber paper(Pt@Mo_(2)C/CFP)electrocatalyst has Pt content as low as 0.03 mg cm^(-2),which can achieve overpotential of 17 mV at 10 mA cm^(-2),surpassing the commercial Pt/C.Moreover,it exhibits an excellent sustained stability for over 100 h at 500 mA cm^(-2)in a practical alkaline water electrolyzer.The work offers new opportunities to design and synthesize superior performance electrocatalysts for the alkaline HER.
基金supported by the National Natural Science Foundation of China(Nos.22171287 and 52303274)Taishan Scholar Project of Shandong Province(No.tsqn202103046)+2 种基金Natural Science Foundation of Shandong Province(No.ZR2022QE175)Young Innovative Science and Technology Support Program for Universities of Shandong Province,P.R.China(Nos.2023KJ280 and 2021KJ014)Fundamental Research Funds for the Central Universities(Nos.24CX07007A and 22CX01002A-1)
文摘Constructing clus ter heterostructures with strongly coupled interfaces is of great importance to accelerating the catalytic reactions that involve multiple intermediates.Herein,a strongly coupled cluster heterostructure composed of platinum and molybdenum carbide(Pt@Mo_(2)C)derived from polyoxometalate clusters is designed to achieve excellent alkaline hydrogen evolution reaction.The Pt@Mo_(2)C cluster exhibits strong electronic interactions between Pt and Mo_(2)C,working together to facilitate the H_(2)O dissociation by concurrently binding intermediates(Pt-H*and Mo-OH*),thus accelerating the kinetics of the rate-determining Volmer step.Theoptimized Pt@Mo_(2)C exhibits a high mass activity of12.1 A·mgpt^(-1),19.2 times higher than that of 20%Pt/C in alkaline media.Moreover,it can be stabilized at a current density of 100 mA·cm^(-2)for more than 200 h.This work demonstrated the superiority of the cluster heterostructures and co-catalytic effect towards the development of highly efficient electrocatalysts.
基金supported by the National Natural Science Foundation of China(No.21801153)Natural Science Foundation of Shandong Province(No.ZR2023MB065)+1 种基金Academic promotion program of Shandong First Medical University(No.2019LJ003)High-level Overseas Talent Workstation of Shandong Province.
文摘Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting.Nowadays,novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development.Under the current requirements to high production capacity and novel synthesis methods of drugs,green synthesis based on strategies with different ways of empowering,advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging.Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes.Polyoxometalates(POMs)are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials,catalysis and medicine.In this review,the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts,alternative reaction equipment based novel synthesis protocols.The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
基金supported by National Natural Science Foundation of China(No.22371278)Funding of Fujian Provincial Chemistry Discipline Alliance+1 种基金Natural Science Foundation of Fujian Province(No.2021J06035)Youth Innovation Promotion Association CAS(No.Y2018081)。
文摘For a long time,researchers have been fascinated by the structurally diverse and high-performance characteristics of polyoxometalates(POMs).Modifying POMs with various types and properties of metals has broadened their applications in fields such as magnetism,luminescence,and catalysis.However,despite the discovery of numerous POM structures doped with transition metal ions,the development of aluminum(Al)as aⅢA group metal in the POM field has been slow.Aluminum,the most abundant metal in nature,offers innate electron-deficient properties that,when combined with highly charged POMs,could introduce novel structures and excellent functionalities like proton conduction to this field.Therefore,this review will address the gap in summarizing Al-containing POMs by categorizing and summarizing the synthesis,structural characteristics,and properties of Al-containing POMs,aiming to provide a theoretical foundation for exploring POM structures doped with Al atoms.The review also analyzes and forecasts the prospects in this field.
基金supported by the National Natural Science Foundation of China(Grant Nos.:92261203,21971106,22171073,22101118,and 22201123)the Central Guided Science and Technology Development Foundation of Liaoning Province,China(Grant No.:2022 JH6/100100036)+1 种基金the Start-up Fund from Southern University of Science and Technology(SUSTech),China,the Stable Support Plan Program of Shenzhen Natural Science Fund,China(Program Contract No.:20200925161141006)the Shenzhen Nobel Prize Scientists Laboratory Project(Shenzhen Grubbs Institute),China(Project No.:C17783101).
文摘Polyoxometalates(POMs)are molecular metal-oxide clusters with precise chemical composition and architecture.Besides their bioactivities,electron-rich POMs have shown potential for enhancing synergistic therapy,such as photothermal therapy(PTT),photodynamic therapy(PDT),and chemo-dynamic therapy(CDT),through near-infrared region(NIR)absorption and redox reactions.
基金Project supported by Institution of Chemical Materials, China Academy of Engineering Physics
文摘A series of novel photocatalysts, H3PW12O40-Y-TiO2 nanocomposites with different H3PW12O40 loading levels （10%-40%） were prepared by impregnation method. And the Y-TiO2 support, doped with yttrium, was synthesized via sol-gel technique. The prepared catalysts were characterized by Fourier transform infrared spectroscopy （FT-IR）, powder X-ray diffraction （XRD）, nitrogen adsorption-desorption analysis and scanning electron microscopy （SEM）. The processes allowed obtaining Keggin structure and crystallized anatase with large BET surface area as well as uniform distribution. The effects of H3PW12O40 loadings, catalyst dose, initial pH and concentration of dye solution on the degradation kinetics of methyl orange under UV light （λ≥365 nm） were discussed. Kinetics studies showed that the photocatalytic degradation of methyl orange fitted the apparent first-order reaction. Methyl orange was totally degraded in 21 min under optimum conditions： 20% loading, 0.03 g dose and pH 1.0. The catalyst was stable and easily to be separated from reaction system for recovery.
基金supported by the Basic Research Foundation of Beijing Institute of Technology (20110242020)
文摘A novel supported polyoxometalate （POM）, phosphotungstic acid immobilized into yttrium-doped TiO2 （HPW-Y-TiO2） nano photocatalyst was prepared via sol-gel and impregnation method. The samples were characterized using Fourier transform in- frared spectroscopy （FT-IR）, X-ray diffraction （XRD） and N2 absorption-desorption analysis. The results showed that the supported POM exhibited Keggin structure and anatase phase with large BET surface area. The influences of inorganic anions and organic addi- tives on the photocatalytic degradation of azo dye methyl orange with HPW-Y-TiO2 as photocatalyst under UV light （2〉365 urn） were investigated. Results showed that inorganic anions CI, 504^2-, CO32 and NO3 had inhibition effect on the degradation of methyl orange. A great enhancement of degradation rate was obtained while H202 and ethyl alcohol were applied. The degradation rates improved with the increase of H202 concentration. The optimum additive amount of ethyl alcohol was 0.5 mol/L. The possible mechanisms of the effects of additives on methyl orange degradation were discussed.
基金supported by the National Natural Science Foundation of China(21776077)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning+3 种基金the Shanghai Rising-Star Program(17QA1401200)the Open Project of SKLOCE(SKL-Che-15C03)the Shanghai Natural Science Foundation(17ZR1407300 and 17ZR1407500)the State Key Laboratory of Organic-Inorganic Composites(oic201801007)。
文摘Heterogeneously catalyzed hydrolytic dehydrogenation of ammonia borane is a remarkable structure sensitive reaction. In this work, a strategy by using polyoxometalates(POMs) as the ligands is proposed to engineer the surface and electronic properties of Pt/CNT catalysts toward the enhanced hydrogen generation rate and durability. Three kinds of POMs, i.e., silicotungstic acid(STA), phosphotungstic acid(PTA)and molybdophosphoric acid(PMA), are comparatively studied, among which the STA shows positive effects on the catalytic activity and durability. A catalyst structure-performance relationship is established by a combination of kinetic and isotopic analyses with multiple characterization techniques, such as HAADF-STEM, EDS, Raman spectroscopy and XPS. It is shown that the STA compared to the other two POMs can increase the Pt binding energy and thus promote the reaction. The insights demonstrated here could open a new avenue for boosting the reaction by employing the POMs as the ligands to engineer the catalyst electronic properties.
基金supported by the National Key Basic Research Program of China(973 program,2013CB934101)National Natural Science Foundation of China(21433002,21573046)+1 种基金China Postdoctoral Science Foundation(2016M601492)International Science and Technology Cooperation Projects of Guangxi(15104001-5)~~
文摘Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for developing a lignin catalytic decomposition process could be developed by exploring the transformation mechanisms of various model compounds. Herein, decomposition of a lignin model compound, 2-phenoxyacetophenone （2-PAP）, was investigated over several ce-sium-exchanged polyoxometalate （Cs-POM） catalysts. Decomposition of 2-PAP can follow two dif-ferent mechanisms： an active hydrogen transfer mechanism or an oxonium cation mechanism. The mechanism for most reactions depends on the competition between the acidity and redox proper-ties of the catalysts. The catalysts of POMs perform the following functions： promoting active hy-drogen liberated from ethanol and causing formation of and then temporarily stabilizing oxonium cations from 2-PAP. The use of Cs-PMo, which with strong redox ability, enhances hydrogen libera-tion and promotes liberated hydrogen transfer to the reaction intermediates. As a consequence, complete conversion of 2-PAP （〉99%） with excellent selectivities to the desired products （98.6% for phenol and 91.1% for acetophenone） can be achieved.
文摘Bismuth‐based photocatalysts are a class of excellent visible‐light photocatalysts;however,their redox activity is relatively poor and the efficiency of photogenerated carrier separation is low,limiting their development and application in the field of photocatalysis.To address these issues,a series of polyoxometalate PW_(12)O_(40)^(3–)‐doped Bi_(2)O_(3–x)/Bi Schottky photocatalysts PW_(12)@Bi_(2)O_(3–x)/Bi‐n(PBOB‐n,where n is the amount of NaBH4,i.e.,6,12,18,24,and 48 mg)were prepared by a simple electrospinning/calcination/in‐situ NaBH4 reduction method.In this composite photocatalyst,the doping of PW_(12) could effectively adjust the electronic structure of Bi_(2)O_(3–x) and improve its redox properties.As a shallow electron trap,PW_(12) promoted the separation of the photogenerated carriers.Furthermore,desirable Schottky junction between the metal Bi nanoparticles and PW_(12)@Bi_(2)O_(3–x) further accelerated the separation of the photogenerated carriers.The synergistic effect of the aforementioned factors endowed PBOB‐n with excellent photocatalytic activity.Among the samples,PBOB‐18 exhibited superior photocatalytic activity.Under visible‐light irradiation,93.7%(20 mg catalyst)of 20 ppm tetrabromobisphenol A(TBBPA,20 mL)was degraded in 60 min.Its activity was 4.4 times higher than that of Bi_(2)O_(3).PBOB‐18 also exhibited an ultrahigh photocatalytic performance for the removal of NO.Its removal rate(600 ppb)reached 83.3%in 30 min,making it one of the most active Bi‐based photocatalysts.Furthermore,the photocatalytic mechanisms of PBOB‐18 for TBBPA and NO have been proposed.This work provides a new direction and reference for the design of low‐cost,efficient,stable,and versatile photocatalysts.
基金Project supported by China Academy of Engineering Physics (6260107025)
文摘A series of photocatalysts, K11[Ln(PW11O39)2]/PVA (Ln=La, Ce, Pr, Nd, Sm) were prepared by K11[Ln(PW11O39)2] (Ln=La, Ce, Pr, Nd, Sm) containing five kinds of lanthanides and polyvinyl alcohol as the support. The catalysts obtained were characterized by Fourier transform infrared spectra, UV-vis spectra, powder X-ray diffraction, and scanning electron microscopy, indicating that the structure of K11[Ln(PW11O39)2] and polyvinyl alcohol remained intact, respectively. The photocatalysts exhibited efficient catalytic activity to degrade methyl orange, Congo Red, Ponceau 2R. The maximal degradation conversions of the three kinds of dyes were 99.58%, 47.61%, 72.42%, respectively.
基金supported by the National Natural Science Foundation of China(Nos.21871224,92161104,92161203 and 21721001)Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM No.RD2021040301)。
文摘Three sandwich-like[Ln_(2)Fe_(2)(B-α-FeW_9O_(34))_(2)]^(10-) clusters(Ln_(2)Fe_(4),Ln=Dy(1),Ho(2),and Y(3)) were obtained by reacting Na_9[B-α-SbW_9O_(33)],Ln_(2)O_(3),FeCl_(3)·6H_(2)O and KH_(2)PO_(4).The[B-α-FeW_9O_(34)]^(11-) units were formed via the in situ conversion of lacunary polyoxometalates(POM)[B-α-SbW_9O_(33)]^(9-)and the Ln^(3+)ions were generated from the slow dissolution of Ln_(2)O_(3),both of which play important roles in the synthesis of Ln_(2)Fe_(4).Ln_(2)Fe_(4) is the first 3d-4f cluster assembled from d-metal heteroatom-containing POM.The Dy_(2)Fe_(4) cluster exhibits single-molecule magnet properties with an 80 K energy barrier in an optimal DC field.Cyclic voltammetry tests and controlled-potential coulometry experiments show that the polyoxometalate Fe heteroatom in clusters 1-3 is also electrochemically active.
基金financially supported by the National Natural Science Foundation of China (No.21801153)Academic promotion program of Shandong First Medical University (N0.2019LJ003)。
文摘Health care and medical care have always been dominant topics in human society.The field of precision medicine,iatrotechnics revolution and timely on-demand detection have continued to evolve in response to increasing demands from the society.Furthermore,the emergence of innovative materials and their applications offer promising prospects for advancing global health.Polyoxometalates(POMs)are negatively-charged molecular metal oxides with well-defined structures,beautiful geometries and nanoscale sizes.Owing to their vast diversity in composition,structure,nuclearity and charge,they constitute a significant subcategory of inorganic clusters that contain bridging oxygen atoms between two or more metal ions.Nowadays,POMs based nanocomposites have been widely applied in the field of disease diagnosis,anticancer therapy and antibacterial therapy as new generation bioactive materials.In this review,the recent advances of POMs based nanocomposites in bioapplications are summarized and the future perspectives are discussed.
基金supported by the National Natural Science Foundation of China(Nos.22171073.21971224 and U1804253)the Natural Science Foundation of Henan Province(No.202300410246).
文摘The visible-light-induced selective oxidation of ubiquitous C–H bonds into valuable C=O bonds under aerobic conditions is one of the most attractive approaches for the construction of carbonyl-containing molecules.In this work,two transition metal-containing Nb/W mixed-addendum POMs dimers with the formula of K_(2)Na_(2)H_(5)[(Fe(H_(2)O)_(4))_(3)(P_(2)W_(15)Nb_(3)O_(62))_(2)]·24H_(2)O(POM[Fe])and K_(2)Na_(3)H_(4)[(Cr(H_(2)O)_(4))_(3)(P_(2)W_(15)Nb_(3)O_(62))_(2)]·32H_(2)O(POM[Cr])have been synthesized and characterized by various analytical and spectral techniques.POM[Fe]was proved to be an efficient photocatalyst for benzylic C–H oxidation under visible light and using oxygen as an oxidant to produce the corresponding carbonyl complex in good yields.A plausible mechanism involving superoxide radical was proposed for the catalytic reaction.POM[Fe]showed good reusability in the recycling experiments.IR spectroscopy and XRD analysis indicate that POM[Fe]can retain its integrity after catalysis.
基金supported by National Natural Science Foundation of China (Nos. 92161111, 21901037, 21901038)Shanghai Pujiang Program (No. 19PJ1400200)+1 种基金the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher LearningFundamental Research Funds for the Central Universities (No. 2232019G-07)。
文摘Crystalline porous ionic salts(CPISs) represent a new type of porous materials constructed by electrostatic interaction, however, synthesis of CPISs bearing pre-designed functionality while exhibiting permanent porosity is still challenging. Herein we report the facile synthesis of a series of CPISs 1-3 built from photocatalytic-active polyoxometalate(POM) clusters and cationic Zr-based capsules, which showed open porous frameworks with BET surface area up to 33 m^(2)/g and high activity and selectivity for photodriven aerobic oxidation of alcohols to aldehydes. Compared with the pristine POM cluster {W10}, 1 can promote the reaction in much higher efficiency due to the concerted catalysis of preinstalled {W10} and Zr-based capsule together with open channels. This work highlights the advantage of CPISs as porous heterogeneous catalysts in organic transformation, and may shed light on the rational design of more delicate CPISs-derived functional materials.
基金supported by the National Natural Science Foundation of China(No.22001034)Jiangxi Provincial Natural Science Foundation(No.20212BAB213001)the Open Fund of the Jiangxi Province Key Laboratory of Synthetic Chemistry(No.JXSC202008)。
文摘Polyoxometalates(POMs)have conducive properties such as controlled Bronsted and Lewis acidity,high thermal stability,nontoxic nature,tunable solubility,and less corrosiveness.POMs have been extensively applied in catalytic organic reactions and have an exciting prospect for industrial applications.This review summarized recent progress in the application of POMs as acid catalysts for various organic reactions including C-C bond formation,C-N bond formation,C-O bond formation,heterocyclic synthesis reactions,cyanosilylation and hydrolysis reactions.Various POMs catalysts including heteropoly acids(HPAs)and cationic functionalized HPAs with Bronsted acidity,HPAs supported on non-precious metal support with Bronsted acidity(or both Bronsted and Lewis acidity),transition metal substituted POMs with Lewis acidity were applied in above reactions.This review attempts to provide up-to-date information about POMs acid-catalyzed organic reactions and propose future prospects.
基金This project was supported by the National Natural Science Foundation of China(20071004)Beijing Natural Science Foundation(2002007)Scientific Research Foundation for the Retumed Overseas Chinese Scholars,State Education Ministry,to KZW.
文摘Hybrid self-assembled multilayer films were prepared by alternate adsorption of 1,10-diaminodecane (1,10-DAD) and Keggin polyoxometalates of SiW12O404-, SiW11VO405-, and PMo12O403-, respectively. The films were reproducibly grown at each adsorption cycle as monitored by UV spectroscopy.
基金financially supported by the National Key Basic Research Program of China(grant no.2020YFA0406101)National Natural Science Foundation of China(grant nos.22171041,22071020,21901035,22271043)+1 种基金Natural Science Foundation of Jilin Province Science and Technology Department(grant nos.20230508094RC,20220101045JC)the Fundamental Research Funds for the Central Universities(grant no.2412021QD008)
文摘Solar vapor generation(SVC)represents a promising technique for seawater desalination to alleviate the global water crisis and energy shortage.One of its main bottleneck problems is that the evaporation efficiency and stability are limited by salt crystallization under high-salinity brines.Herein,we demonstrate that the 3D porous melamine-foam(MF)wrapped by a type of self-assembling composite materials based on reduced polyoxometalates(i.e.heteropoly blue,HPB),oleic acid(OA),and polypyrrole(PPy)(labeled with MF@HPB-PPy_(n)-OA)can serve as efficient and stable SVC material at high salinity.Structural characterizations of MF@HPB-PPy_(n)-OA indicate that both hydrophilic region of HPBs and hydrophobic region of OA co-exist on the surface of composite materials,optimizing the hydrophilic and hydrophobic interfaces of the SVC materials,and fully exerting its functionality for ultrahigh water-evaporation and anti-salt fouling.The optimal MF@HPB-PPy_(10)-OA operates continuously and stably for over 100 h in 10wt%brine.Furthermore,MF@HPB-PPy_(10)-OA accomplishes complete salt-water separation of 10wt%brine with 3.3kgm^(-2)h^(-1)under 1-sun irradiation,yielding salt harvesting efficiency of 96.5%,which belongs to the record high of high-salinity systems reported so far and is close to achieving zero liquid discharge.Moreover,the low cost of MF@HPB-PPy_(10)-OA(2.56$m^(-2))suggests its potential application in the practical SVC technique.
基金Supported by the National Natural Science Fund for Distinguished Young Scholars of China (No. 20725101)the NNSFC (Nos. 50872133 and 20821061)+2 种基金the 973 Program (No. 2006CB932904)the NSF of Fujian Province (No. E0510030)the Knowledge Innovation Program of CAS
文摘Two new hybrid polyoxotungstates, [Co（2,2＇-bipy）3][a-H5PW11CoO40]-3H2O 1 and [Fe（2,2＇-bipy）3]2[a-HBW12O40]-2.5H2O 2 （2,2＇-bipy = 2,2＇-dipyridyl）, have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray structural analyses. The results of X-ray crystallography analyses exhibit that 1 consists of one a-Keggin anion [a-H5PW11CoO40]2- and one isolated [Co（2,2＇-bipy）3]2＋ complex, while 2 is constructed from one a-Keggin anion [a- HBW12O40]4- and two isolated [Fe（2,2＇-bipy）3]2＋ cations. The data for 1： orthorhombic system, space group Pbcn, a = 16.062（6）, b = 27.278（10）, c = 16.951（6）A, V = 7427（5）A3 and Z = 4; and those for 2： triclinic system, space group P1, a = 13.787（3）, b = 17.857（5）, c = 18.918（5）A, a = 88.009（12）, β = 72.768（10）, γ = 74.935（10）°, V = 4291（2）A3 and Z = 2.
