Photocatalytic water splitting and carbon dioxide photoreduction are considered eff ective strategies for alleviating the energy crisis and environmental pollution.Polynuclear metal-oxo clusters possess excellent elec...Photocatalytic water splitting and carbon dioxide photoreduction are considered eff ective strategies for alleviating the energy crisis and environmental pollution.Polynuclear metal-oxo clusters possess excellent electron storage/release ability and unique catalytic properties via intermetallic synergy,which enables them with great potential in environmentally friendly photosynthesis.Importantly,metal-oxo clusters with precise structure can not only act as high-effi ciency catalysts but also provide well-defi ned structural models for exploring structure-activity relationships.In this review,we systematically sum-marize recent progress in the catalytic application of polynuclear metal-oxo clusters,including polyoxometalate clusters,low-cost transition metal clusters,and metal-oxo-cluster-based metal-organic frameworks for water splitting and CO_(2)reduction.Furthermore,we discuss the challenges and solutions to the problems of polynuclear metal-oxo clusters in photocatalysis.展开更多
The fascinating chemical structure and broad application prospect of Keggin-type polyoxometalates(POMs)have attracted many chemists to explore and discover continuously.Unlike the traditional Keggin,larger metal atomi...The fascinating chemical structure and broad application prospect of Keggin-type polyoxometalates(POMs)have attracted many chemists to explore and discover continuously.Unlike the traditional Keggin,larger metal atomic radius,higher metal coordinated numbers,lower metal valence states and other features allow the group IVB metal-based Keggin(IVB-Keggin)more space and unknown in terms of structure and performance.Herein,density functional theory(DFT)calculations were performed to explore the influences including cores,shells,caps,and terminal ligands,et al.on IVB-Keggin,and analyze the possibility of novel structure synthesis.From the perspective of multi-layer onion-like clusters,molecular energy level,host-guest interaction energy,surface charge and covalent bond polarity can be further adjusted to achieve the oriented design of functional IVB-Keggin.These insights are expected to provide theoretical support for experimental synthesis,opening a new perspective to understand the growth of Keggin.展开更多
A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 · 6H2O and 1,10-phenathroline (1,10-phen) as raw mate...A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 · 6H2O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to mono-clinic P21/n space group, a= 1.2952(2), b = 1.6659(10), c= 1.3956(12) nm, β=106.273(8)°, V = 2.8906(5) nm3, Z = 2. 5604 observable reflections (/>2σ(/)) were used for structure resolution and refinements to converge to final R1 = 0.0414, wR2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as ξ-isomer). The feature of ξ-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octa-hedra located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MovI atoms. Each ξ-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.展开更多
Owing to the need for regenerant and self-reduction problem,the hydrogen performance of sub-nano-sized trinuclear iron-oxo complexes is still far from satisfied with affordability and practicality.Herein,two binary ph...Owing to the need for regenerant and self-reduction problem,the hydrogen performance of sub-nano-sized trinuclear iron-oxo complexes is still far from satisfied with affordability and practicality.Herein,two binary photocatalytic systems based on trinuclear metal-oxo complexes have been first constructed and experimentally confirmed to be competent for seawater hydrogen evolution(715.4and271.9μmol of hydrogen can be found,respectively,after 48h).Notably,chloride ions act as the hole catcher and move into the gas phase in the stable form of chlorine.Similar to heterogeneous structures,homogeneous systemsnot only enhance the hydrogen performance while ensuring the stability of metal-oxo complexes,but also shorten the consumption of photogenerated carriers by dissolved impurities in the seawater.This new attempt of building pluralistic sub-nanometric systems may offer novel design strategies with noble-metal-free catalysts and low-cost candidates for traditional semiconductor materials in enhancing photocatalytic efficiency and performing chlorine evolution from seawater splitting.展开更多
The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compou...The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857（3）, b = 12.9619（18）, c = 20.204（3） A, β = 105.692（2）°, V= 6015.0（14） A3, Z = 4, Dc= 2.473 g/cm^3, M,.= 2239.68, F（000） = 4432, R = 0.0725, wR = 0.1524 and GOOF= 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO4^3- guest.展开更多
Accompanying an annual increase in cancer incidence,the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks.In this study,the oxidation of methotr...Accompanying an annual increase in cancer incidence,the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks.In this study,the oxidation of methotrexate(MTX),a typical anticancer drug with ubiquitous occurrence and multi-endpoint toxicity,by ferrate(VI)(Fe(VI))and permanganate(Mn(VII)))was investigated in water.Fe(VI)exhibited a higher reactivity with MTX(93.34 M^(−1) s^(−1))than Mn(VII)(3.01 M^(−1) s^(−1)) at pH 8.0.The introduction of Cu(II)and Fe(III)at 1.0 mM improved the removal efficiency of 5.0μM MTX by 100.0μM Fe(VI)from 80%to 95%and 100%after 4 min,respectively.Seven oxidized products(OPs)were identified during oxidative treatments,while OP-191 and OP-205 were characterized as specific products for Fe(VI)oxidation.Initial ketonization of the L-glutamic acid moiety and cleavage of the peptide bond of MTX were proposed.Additionally,a multi-endpoint toxicity evaluation indicated no genotoxicity,neurotoxicity,or endocrine-disrupting effects of MTX and its OPs.Particularly,serious developmental toxicity in zebrafish larvae was observed in the treated MTX solutions.Based on the acute and chronic aquatic toxicity prediction,OP-190,OP-192,OP-206,and OP-208 were deemed toxic or very toxic compared to harmful MTX.Furthermore,the reduced biodegradability index from 0.15(MTX)to−0.5 to−0.2(OP-192,OP-206,and OP-468)indicated the formation of lower biodegradable OPs.Overall,this study suggests that Fe(VI)and Mn(VII)oxidation are promising treatments for remediating anticancer drug-contaminated water.However,the environmental risks associated with these treatments should be considered in the evaluation of water safety.展开更多
基金supported by National Natural Science Foundationof China(Grant No.21671113)the Science and Technology of Henan province in 2018(No.182102310873)+2 种基金2019 Special Project of Nanyang Normal University(Nos.2019ZX009 and 2019QN011)Project of Young Backbone Teachers in Colleges and Universities of Henan Province(No.2020GGJS180)2019 Henan Higher Education Teaching Reform Research and Practice Project(No.2019SJGLX093Y).
文摘Photocatalytic water splitting and carbon dioxide photoreduction are considered eff ective strategies for alleviating the energy crisis and environmental pollution.Polynuclear metal-oxo clusters possess excellent electron storage/release ability and unique catalytic properties via intermetallic synergy,which enables them with great potential in environmentally friendly photosynthesis.Importantly,metal-oxo clusters with precise structure can not only act as high-effi ciency catalysts but also provide well-defi ned structural models for exploring structure-activity relationships.In this review,we systematically sum-marize recent progress in the catalytic application of polynuclear metal-oxo clusters,including polyoxometalate clusters,low-cost transition metal clusters,and metal-oxo-cluster-based metal-organic frameworks for water splitting and CO_(2)reduction.Furthermore,we discuss the challenges and solutions to the problems of polynuclear metal-oxo clusters in photocatalysis.
基金financially supported by the National Natural Science Foundation of China(NSFC,Nos.22225109,22071109,92061101,22173016 and 22301084)the China Postdoctoral Science Foundation(No.2023M741232)。
文摘The fascinating chemical structure and broad application prospect of Keggin-type polyoxometalates(POMs)have attracted many chemists to explore and discover continuously.Unlike the traditional Keggin,larger metal atomic radius,higher metal coordinated numbers,lower metal valence states and other features allow the group IVB metal-based Keggin(IVB-Keggin)more space and unknown in terms of structure and performance.Herein,density functional theory(DFT)calculations were performed to explore the influences including cores,shells,caps,and terminal ligands,et al.on IVB-Keggin,and analyze the possibility of novel structure synthesis.From the perspective of multi-layer onion-like clusters,molecular energy level,host-guest interaction energy,surface charge and covalent bond polarity can be further adjusted to achieve the oriented design of functional IVB-Keggin.These insights are expected to provide theoretical support for experimental synthesis,opening a new perspective to understand the growth of Keggin.
文摘A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 · 6H2O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to mono-clinic P21/n space group, a= 1.2952(2), b = 1.6659(10), c= 1.3956(12) nm, β=106.273(8)°, V = 2.8906(5) nm3, Z = 2. 5604 observable reflections (/>2σ(/)) were used for structure resolution and refinements to converge to final R1 = 0.0414, wR2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as ξ-isomer). The feature of ξ-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octa-hedra located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MovI atoms. Each ξ-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.
基金This work was supported by the National Natural Sci-ence Foundation of China(No.52071171)Liaoning Revitalization Talents Program-Pan Deng Scholars(XLYC1802005)+6 种基金Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Natural Science Fund of Liaoning Province for Excellent Young Scholars(2019-YQ-04)Key ProjectofScientificResearchoftheEducationDepartment of Liaoning Province(LZD201902)Shenyang Science and Technology Project(21-108-9-04)Australian Research Council(ARC)through Future Fellowship(FT210100298)Discovery Project(DP220100603)Linkage Project(LP210200504)schemes,CSIRO Energy Centre and Kick-Start Project.
文摘Owing to the need for regenerant and self-reduction problem,the hydrogen performance of sub-nano-sized trinuclear iron-oxo complexes is still far from satisfied with affordability and practicality.Herein,two binary photocatalytic systems based on trinuclear metal-oxo complexes have been first constructed and experimentally confirmed to be competent for seawater hydrogen evolution(715.4and271.9μmol of hydrogen can be found,respectively,after 48h).Notably,chloride ions act as the hole catcher and move into the gas phase in the stable form of chlorine.Similar to heterogeneous structures,homogeneous systemsnot only enhance the hydrogen performance while ensuring the stability of metal-oxo complexes,but also shorten the consumption of photogenerated carriers by dissolved impurities in the seawater.This new attempt of building pluralistic sub-nanometric systems may offer novel design strategies with noble-metal-free catalysts and low-cost candidates for traditional semiconductor materials in enhancing photocatalytic efficiency and performing chlorine evolution from seawater splitting.
基金This work was supported by the Science and Technology Development Foundation of Fuzhou University (No.2004-xq-05)the Scientific Research Foundation of Fujian Provincial Education Department (No. JB04010)
文摘The novel vanadophosphate （DETAH）（DETAH3）3 [V18O42（PO4）]·（PO4）·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857（3）, b = 12.9619（18）, c = 20.204（3） A, β = 105.692（2）°, V= 6015.0（14） A3, Z = 4, Dc= 2.473 g/cm^3, M,.= 2239.68, F（000） = 4432, R = 0.0725, wR = 0.1524 and GOOF= 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO4^3- guest.
基金supported by the President Research Funds from Xiamen University(No.20720210081)Singapore-China Joint Research Grant Call(NRF-NSFC 3rd Joint Grant Call-Earth Science)(No.41861144023)+1 种基金Natural Science Foundation of China-Joint Fund Project(No.U2005206)Xiamen Municipal Bureau of Science and Technology(No.YDZX20203502000003).
文摘Accompanying an annual increase in cancer incidence,the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks.In this study,the oxidation of methotrexate(MTX),a typical anticancer drug with ubiquitous occurrence and multi-endpoint toxicity,by ferrate(VI)(Fe(VI))and permanganate(Mn(VII)))was investigated in water.Fe(VI)exhibited a higher reactivity with MTX(93.34 M^(−1) s^(−1))than Mn(VII)(3.01 M^(−1) s^(−1)) at pH 8.0.The introduction of Cu(II)and Fe(III)at 1.0 mM improved the removal efficiency of 5.0μM MTX by 100.0μM Fe(VI)from 80%to 95%and 100%after 4 min,respectively.Seven oxidized products(OPs)were identified during oxidative treatments,while OP-191 and OP-205 were characterized as specific products for Fe(VI)oxidation.Initial ketonization of the L-glutamic acid moiety and cleavage of the peptide bond of MTX were proposed.Additionally,a multi-endpoint toxicity evaluation indicated no genotoxicity,neurotoxicity,or endocrine-disrupting effects of MTX and its OPs.Particularly,serious developmental toxicity in zebrafish larvae was observed in the treated MTX solutions.Based on the acute and chronic aquatic toxicity prediction,OP-190,OP-192,OP-206,and OP-208 were deemed toxic or very toxic compared to harmful MTX.Furthermore,the reduced biodegradability index from 0.15(MTX)to−0.5 to−0.2(OP-192,OP-206,and OP-468)indicated the formation of lower biodegradable OPs.Overall,this study suggests that Fe(VI)and Mn(VII)oxidation are promising treatments for remediating anticancer drug-contaminated water.However,the environmental risks associated with these treatments should be considered in the evaluation of water safety.
