DALTON TRANSACTIONS
·
2021
·Vol. 50
·期 37
·12931-12943
·
IF 4.39
Wen-Min Wang,Zhi-Lei Wu,Jian-Zhong Cui
A series of tetranuclear lanthanide-based clusters [Ln4(dbm)6(L)2(CH3OH)4]·2CH3OH (Ln(III) = Gd (1), Dy (2), and Ho (3); H3L = 2-[(2-(hydroxyimino)propanehydrazide)methyl]-2,3-dihydroxybenzaldehyde, Hdbm = dibenzoylmethane) and octanuclear lanthanide-based clusters [Ln8(HL)10(CH3O)4(CH3OH)2]·6CH3OH (Ln(III) = Gd (4), Dy (5)) were assembled using a polydentate Schiff-base ligand H3L and two different β-diketone salts via a solvothermal method, and their structures and magnetic properties have been characterized. Interestingly, β-diketones play an important role in assembling and affecting the structures of Ln4 to Ln8 clusters. This is the first use of β-diketone to affect the structures of polynuclear Ln(III)-based clusters from linear-shaped Ln4 clusters to Ln8 clusters. Magnetic studies revealed that antiferromagnetic interactions exist in clusters 1-Gd4 and 4-Gd8. More importantly, clusters 1-Gd4 and 4-Gd8 display significant cryogenic magnetic refrigeration properties (−ΔSm = 24.88 J kg−1 K−1 for 1-Gd4 and −ΔSm = 32.52 J kg−1 K−1 for 4-Gd8); the results show that cluster 4-Gd8 exhibits a larger magnetocaloric effect than 1-Gd4. Cluster 2-Dy4 shows remarkable single-molecule magnet (SMM) behavior (ΔE/kB = 67.5 K and τ0 = 3.06 × 10−7 s) under a zero dc field, and 5-Dy8 exhibits a field-induced SMM-like behavior (ΔE/kB = 39.83 K and τ0 = 2.12 × 10−7 s) under a 5000 Oe dc field.
研究领域:
无机化学
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材料科学
·
物理化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2019
·
IF 4.85
Wei Wang,Mehran Amiri,Tao Huang,Lev N. Zakharov,Yining Zhang,May Nyman
Isolating Fe(III) clusters from water without stabilizing ligands is significantly challenged by the high acidity of Fe3+-bound water, leading to uncontrolled precipitation of iron oxyhydroxides. Here we demonstrate a freeze-drying solvent-exchange method that enabled the isolation of a metastable Fe(III) sulfate decameric cluster formulated [Fe10O2(SO4)12(OCH3)2]·14CH3OH (Fe10). Without stabilization by solvent-exchange, the aqueous species undergoes rapid conversion to the iron sulfate mineral schwertmannite. Monitoring the hydrolysis process from cluster intermediates to schertmannite by small-angle X-ray scattering, we observe the progression from Fe10 to 37 Å soluble nanoparticles prior to the precipitation process. This condensation behavior of Fe10 is further exploited to develop a simple laboratory synthesis of schwetmannite. In addition, we demonstrate the versatility of the freeze-drying solvent-exchange method by isolating Al(III), Zn(II), and Cd(II) substituted Fe(III) sulfate clusters. The freeze-drying solvent-exchange method provides a unique opportunity to isolate cluster intermediates and models to aid in our understanding of metal-ion hydrolysis processes in environmental, material science, and geological studies.
研究领域:
环境科学
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材料科学
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地质学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INORGANICA CHIMICA ACTA
·
2022
·
IF 3.118
Wei Wang,Jing-Zhe Li,Shi-Jian Luo,Zi-Xuan Yao,Kuan-Guan Liu
Using the atomic precisely structurally characterized clusters as electrocatalysts can provide some possible structure information about the active intermediate during the electrocatalytic N 2 reduction reaction (NRR) process. A Cu4 cluster, named [(bpy) 4 Cu 4 (C 10 H 8 SO 3 ) 4 (OH) 4 ]•4H 2 O ( 1 ), has been synthesized and fully characterized by IR, SXRD, XPS, EPR, et al. Single crystal structural analysis reveals that the core structure of the cluster has a step-scheme conformation with two μ 2 -OH and two μ 3 -OH groups. Electro-catalysis studies of this cluster show that it can achieve a highest NH 3 yield of 2.18 μg h −1 mg −1 and a FE of 0.97 % at −0.6 V. The excellent NRR performance may be attributable to the additional μ 3 -OH groups, based on the contrastively study of the other electrocatalysts of the Cu powder and the Cu 2 complex, named [(μ 2 -OH)(μ 2 -Cl)(bpy) 2 Cu 2 Cl 2 ] ( 2 ), with one μ 2 -OH group in its structure. This work provides some structure information about the possible active sites during the NRR process and inspires us to develop new cluster as efficient electrocatalysts for advancing sustainable NH 3 production. Using the atomic precisely structurally characterized clusters as electrocatalysts can provide some possible structure information about the active intermediate during the electrocatalytic N 2 reduction reaction (NRR) process. A Cu4 cluster, named [(bpy) 4 Cu 4 (C 10 H 8 SO 3 ) 4 (OH) 4 ]•4H 2 O ( 1 ), has been synthesized and fully characterized by IR, SXRD, XPS, EPR, et al. Single crystal structural analysis reveals that the core structure of the cluster has a step-scheme conformation with two μ 2 -OH and two μ 3 -OH groups. Electro-catalysis studies of this cluster show that it can achieve a highest NH 3 yield of 2.18 μg h −1 mg −1 and a FE of 0.97 % at −0.6 V. The excellent NRR performance may be attributable to the additional μ 3 -OH groups, based on the contrastively study of the other electrocatalysts of the Cu powder and the Cu 2 complex, named [(μ 2 -OH)(μ 2 -Cl)(bpy) 2 Cu 2 Cl 2 ] ( 2 ), with one μ 2 -OH group in its structure. This work provides some structure information about the possible active sites during the NRR process and inspires us to develop new cluster as efficient electrocatalysts for advancing sustainable NH 3 production.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Optical Materials
·
2025
·
IF 7.2
Chang Gu,Tao Wang,Xian Qin,Xiaogang Liu
Scintillators are essential in applications, such as homeland security, nuclear physics, and geological exploration. However, conventional scintillators often suffer from degradation under polar chemical conditions, resulting in scintillation quenching and structural decomposition. Here, a molecular engineering strategy is demonstrated to enhance scintillator stability and performance through halogen-bonded lattice reconstruction. The synthesis of a copper cluster scintillator, (X-MBA) 4 Cu 4 I 4 (X: Br or Cl, MBA: S -methylbenzylamine) is reported, where halogen bonding improves lattice symmetry and rigidity, effectively suppressing electron-phonon coupling and defect trapping. The halogenated copper clusters exhibit a photoluminescence quantum yield of ≈90%, a 13-fold increase in light yield, and an X-ray detection limit of 28.8 nGy air s −1 , outperforming halogen-free counterparts. These scintillators maintain their structural integrity and performance even after prolonged exposure to polar chemical solvents. The combination of molecular design and structural robustness enables high-resolution X-ray imaging (22 lp mm −1 ) across various chemical environments, paving the way for high-performance scintillators with exceptional durability and efficiency.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Hui-Min Zeng,Mengyuan Cheng,Weimin Xuan,Yongge Wei
Cyclic compounds are appealing owing to their intrinsic porous structures and facile accessibility as building blocks (BBs) for fabricating high-order assemblies. Nevertheless, the modular synthesis of such molecular entities and their subsequent controlled assembly are still very challenging. Herein, we report the synthesis of a gigantic molybdenum blue (MB) wheel {Mo158} (1), featuring a skirt-shaped structure dimerized from {Mo79}. {Mo79} exhibits an unprecedented octameric architecture built from eight sets of {Mo8} BBs, and the controlled assembly of this smallest member in the MB library is achieved by proper wheel contraction induced by {Mo1} and edge-sharing {Mo2} BBs. Moreover, {Mo158} can function as a 4-connected giant synthon, connecting with adjacent four clusters in a controlled manner via four Mo–O–Mo bridges, resulting in a high-order architecture with a 2D layer structure. In addition to single-crystal X-ray diffraction, {Mo158} is fully characterized by a variety of spectroscopies, allowing for the unambiguous determination of its structure and formula. This work not only enriches the family of gigantic clusters but also demonstrates their potential for constructing more complex assemblies.
研究领域:
无机化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2021
·
IF 3.196
Jingyan Zhu,Baolin Liu,Weibing Zhang,Jun Jiang,Xinhua Li
Single-molecule magnets in cobalt clusters is much less well known than it is in manganese(II)/(III)/(IV) clusters. To explore new types of cobalt clusters and their potential applications, a new mixed valence coordination polymer ([Co(III) 3 Co(II) 2 (mba) 6 (Hdtba) (H 2 O) 4 ] n , H 2 dtba=2,2’-dithiodibenzoic acid, H 2 mba=2-mercaptobenzoic acid) ( 1 ) is constructed by employing cobalt chloride hexahydrate and H 2 mba as starting reactants under hydrothermal conditions. Single-crystal XRD studies indicate that 1 consists of a trinuclear cobalt(III)-sulfur cluster moiety and two discrete cobalt(II) nodes, which result in the formation of a covalent three-dimensional complex network. Similarly, the cobalt(III) cluster moiety acts as a building unit in this infinite coordination polymer 1 instead of the discrete and tiara-like clusters previously reported in the literature. Magnetic studies show its slow magnetic relaxation in the absence of an applied dc field, which is characteristic behavior of single-ion magnets, caused by the individual Co(II) ions.
研究领域:
无机化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2017
·
IF 5.401
Man-Qing Yang,Cai-Ping Zhou,Yun Chen,Jian-Jiang Li,Cheng-Hui Zeng,Shengliang Zhong
A new dinuclear europium cluster (Eu-cluster) is synthesized and the exact structure is determined by single-crystal X-ray diffraction. The formula of the Eu-cluster is determined to be [Eu 2 (4-Msal) 6 (phen) 2 (H 2 O) 2 ] (4-Msal = 4-methylsalicylic acid, phen = phenanthroline), it crystallizes in the triclinic space group P -1, with a = 9.1193(8) Å, b = 13.0855(10) Å, c = 14.0981(9) Å, α = 103.159(6)°, β = 94.192(6)°, γ = 100.632(7)°, V = 1598.3(2) Å 3 and Z = 1. Further investigation reveals that the Eu-cluster is a highly sensitive and selective methylmercury (CH 3 Hg + ) sensor. To the best of our knowledge, this is the first CH 3 Hg + sensor based on lanthanide clusters/complexes. The responsive behavior shows the sensing has excellent linearity in 1.4–3.8 μg L −1 μM. The LOD for sensing CH 3 Hg + is 0.8 μg L −1 , which meets the standard of Chinese environmental quality standard for agricultural and industrial water. Interestingly, study also reveals the sensor is applicable in real water sensing.
研究领域:
分析化学
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环境科学
✓ 已验证
DOI
高影响因子
ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY
·
2022
·
IF 7.129
Shihuan Lu,Xizi Li,Bingzhi Yu,Jiafeng Ding,Yuchi Zhong,Hangjun Zhang
Efficient treatment of cyanobacterial blooms in eutrophication waters by safe and reliable nanomaterials is a big challenge for reducing environmental health risks. Herein, a novel strategy combining palladium clusters (Pd n ) with g-C 3 N 4 nanocomposite was presented to achieve high-efficient removal of Microcystis aeruginosa cells through coagulation and breakage. Interestingly, 95.17% of algal cells (initial concentration of 5.6 × 10 6 cells mL −1 ) were promptly removed in the Pd/g-C 3 N 4 (5%) system within only 10 min and without visible light irradiation and persulfate activation. Both the release of potassium ion and microcystin during the removal process and the transmission electron microscope observations of Microcystis aeruginosa cells proved that the integrity of the algal cell membrane was destroyed. The removal of Microcystin-LR (MC-LR) were further confirmed in the next process. Pd metal interaction and breakage against algal cells may cause disruption of algal cells. This study describes a novel technology for the superfast removal of harmful algae and may provide a new insight into the control of cyanobacterial blooms in practical applications.
研究领域:
环境科学
·
微生物学
✓ 已验证
DOI
PubMed
高影响因子
FUEL
·
2024
·
IF 6.7
Caijun Deng,Chaofan Qi,Zongping Xue,Kai Cui,Xiaomin Wu,Guohua Jing,Huawang Zhao
Hydrogen is a promising clean energy source, and formic acid serves as a significant hydrogen storage material. The electrocatalytic reduction of carbon dioxide (ECO 2 RR) is a promising approach to produce fromate. However, the challenge lies in developing high-performance electrocatalysts for the conversion of CO 2 to formate, due to the limited intrinsic activity, conductivity, and the low density of active sites. In this work, we have fabricated highly active and selective CH 3 COO(BiO) (BiOAc) nanosheets. These nanosheets undergo a transformation into Bi clusters-BiO 2 CO 3 during electrolysis, endowing the material with superior electrocatalytic capabilities for CO 2 reduction to formate, with a Faradaic selectivity of over 90 % across a wide potential window from −0.8 to −1.3 V. Additionally, this catalyst can sustain high current densities above 80 mA cm −2 at low applied potentials without compromising selectivity in a H type electron reactor. Both density functional theory (DFT) and in situ attenuated total reflection-infrared spectroscopy (in situ ATR-IR) findings indicate that the Bi 3+ with reduced density facilitate the activation of CO 2 to *CO 2 , while the charge density-enriched Bi 0 atoms in Bi cluster promote the capture of HCO 3 – and enhance subsequent proton-coupled electron transfer reactions. Collectively, these factors significantly reduce the energy barrier for *OCHO formation on BiOAc, thereby enhancing its catalytic activity and Faradaic efficiency for the electroreduction of CO 2 .
研究领域:
材料科学
·
环境科学
·
电化学
✓ 已验证
DOI
高影响因子
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
·
2020
·Vol. 646
·期 15
·1309-1314
·
IF 1.24
Yan Zhang,Jing Fan,Lingzhi Chen,Na Liu,Hongmei Geng
Two new tetranuclear cluster-based compounds, namely [Cd 2 (L1)(H 2 O)(DMA)] n ( 1 ) and [Cd 2 Ba 2 (L2)(H 2 O) 6 (DMA)] n ( 2 ) [H 4 L1 = 3-(3',5'-dicarboxylphenoxy) phthalic acid, H 4 L2 = 6-(3',4'-dicarboxyl-phenoxy) isophthalic acid, DMA = N,N' -dimethylacetamide], were successfully synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analyses. Compound 1 features a two-dimensional (2D) layered framework with tetranuclear [Cd 4 (COO) 6 ] clusters as building subunits, and can be simplified into a binodal (3, 6)-connected kgd topological network with the schläfli symbol of {4 3 } 2 {4 6 ;6 6 ;8 3 }, and compound 2 features a three-dimensional (3D) complicated framework based on heterometallic tetranulear [Cd 2 Ba 2 (COO) 8 ] cluster subunits, and can be simplified into a binodal (3, 6)-connected topological network. In addition, compounds 1 and 2 not only have high thermal stabilities but also show strong luminescent emissions at room temperature.
研究领域:
无机化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2018
·Vol. 5
·期 8
·1787-1794
·
IF 5.106
Yanna Chen,Min Zhang,Cong Hu,Zhihua Yang,Shilie Pan
As the first reported examples of borates in the Zn–Sc–B–O system, Ba2ZnSc(BO3)3 and Ba4Zn5Sc2(BO3)8 were synthesized through a high-temperature solution method. The structure of Ba2ZnSc(BO3)3 can be described as ZnO4 tetrahedra connecting ScO6 octahedra to form a [ZnScO9]13− dimer, which further bonds with seven BO3 triangles to form a 2∞[ZnSc(BO3)3] layer, and the Ba atoms distribute in the voids between the layers. In contrast, in Ba4Zn5Sc2(BO3)8, Zn–O chains composed of 4- and 6-coordinated Zn atoms link with Sc2O8 dimers to form a Zn–Sc–O layer, and the BO3 triangles and Ba atoms fill in the voids between the layers. Interestingly, the special [Zn2(BO3)6]14− cluster is found in Ba2ZnSc(BO3)3, which is different from the 2D layers or 3D frameworks of the Zn–B–O configurations in other zincoborates. Moreover, the lowest-coordinated ScO5 polyhedra, as well as the coexistence of two types of ZnOn units (n = 4 and 6), are observed for the first time in Ba4Zn5Sc2(BO3)8. These fascinating results can promote the design of novel borates with BO3 units and enrich the borate structure chemistry.
研究领域:
材料科学
·
晶体化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Xinze Wu,Xiaoqian Wang,Yalan Hu,Huaixia Chen,Xiaolan Liu,Xueping Dang
This study aimed to investigate the adsorption behaviors of congo red (CR) and methyl orange (MO) on the coordination cluster Zn 5 (H 2 L n ) 6 (NO 3 ) 4 (Zn 5 , H 3 L n = 1,2-bis-(benzo[d]imidazol-2-yl)-ethenol). Due to multinuclear assembly, multinuclear Zn 5 possessed higher electrostatic potential and exhibited 3-fold enhancement in removal efficiency, compared with mononuclear Zn (Zn(H 3 L) 2 , H 4 L = 1,2-bis-(benzo[d]imidazol-2-yl)-1,2-ethanediol). The infrared and X-ray photoelectron spectroscopy and the electrostatic potential analysis indicated that the adsorption mechanism was electrostatic interaction and ion exchange interaction. The adsorption kinetics followed both the pseudo first-order and Bangham models. The pore system analysis and Bangham model suggested that CR and MO could diffuse in the snakelike pores of Zn 5 . The adsorption isotherms complied with the Langmuir isotherm model, and the maximum adsorption capacities for CR and MO are 166.91 and 100.78 mg/g at room temperature. The adsorption process was spontaneous and endothermic, driven by the entropy increase. Based on this research, the multinuclear coordination clusters can be suggested as potential adsorbents for the removal of anionic dyes.
研究领域:
环境科学
·
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）