Inorganic Chemistry Frontiers
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2022
·Vol. 9
·期 18
·4722-4731
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IF 7.779
Zixuan Huang,Lin Zhang,Jiayou Hou,Tengjiao Xu,Bowen Song,Xi Bai,Hai Fu,Peipei Guo
It is highly desirable yet challenging to incorporate open micropores with mass transportation and open active metal sites into metal–organic frameworks (MOFs) for developing novel highly efficient catalysts. Herein, we report a catalyst of low-nuclearity copper-cluster-based micropore MOF, namely H-1e, incorporated with unsaturated Cu(II) centres as open active sites obtained via a highly efficient electrochemical synthesis within 20 minutes. The catalyst H-1e shows potential porosity with 1D open functionalized hexagonal channels for size-selective air oxidation as well as high stability. The electrochemically prepared H-1e exhibits excellent catalytic aerobic oxidation activity for the conversion of alcohols (mini-size) to aldehydes with over 99% selectivity and 99% yield under air conditions, showing excellent reusability and stability. The selective catalytic performances are found to be closely dependent on the suitable aperture size of the 1D channels in H-1e, which provided better beds for the oxidation transformations (confirmed by the computational DFT study). In this study, it offers a simple and potential strategy to construct microporous materials with open active metal sites to promote the catalytic efficiency of MOFs by electrochemical synthesis.
研究领域:
材料科学
·
催化化学
·
电化学
✓ 已验证
DOI
高影响因子
TALANTA
·
2020
·
IF 5.339
Shanliang Song,Yue Zhao,Yang Li,Xudong Yang,Dong Wang,Zhuoqi Wen,Minghui Yang,Quan Lin
The profiling of bacterial metabolism is of great significance in practical applications. Therefore, the development of ultrasensitive and highly selective probe for bacterial metabolism detection and imaging is extremely desirable. Herein, a novel dual-emission pH-response bacterial metabolism detection and imaging probe is successfully developed. This probe consists of large-sized and easily separated SiO 2 microspheres , copper nanoclusters (Cu NCs) with red emission, and carbon dots (CDs) with blue emission through in-situ self-assembly. In this system, the fluorescence of Cu NCs is sensitive to pH change due to their obvious aggregation-induced emission enhancement (AIEE) property, while the blue fluorescence of CDs remained almost stable. Therefore, red fluorescence and blue fluorescence are compounded with different fluorescence intensity at different pH values, and their fluorescence ratio is also different. By observation of composite fluorescence color, the visual colorimetric pH detection can be realized with the change of pH value of 0.2 units. Utilizing this system, we are able to detect bacterial metabolism with high signal-to-noise ratio, and it can also be used for bacterial metabolic imaging. Therefore, the pH-responsive Cu NCs-based dual-emission ratiometric fluorescent probe we constructed can provide new ideas for bacterial detection, antimicrobial sterilization, and biological imaging.
研究领域:
生物化学
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微生物学
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生物成像
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产品关联
DOI
PubMed
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
RARE METALS
·
2021
·Vol. 41
·期 2
·385-395
·
IF 4.003
Feng Ya-Jie,Wang Yang,Wang Kai-Wen,Ma Jiang-Ping,Duan You-Yu,Liu Jie,Lu Xu,Zhang Bin,Wang Guo-Yu,Zhou Xiao-Yuan
Hydrogen, with the merits of zero emissions and high energy density, is one of the promising green energy sources. Seeking for high efficiency and low-cost catalysts is one of the key issues for hydrogen evolution and its practical applications. Nano-structured metal co-catalysts are widely used to improve the photocatalytic performance via surface electronic structure/properties optimization of the catalyst. Herein, we report ultra-fine (~ 1 nm) Cu clusters decorated hydrangea-like TiO 2 systems for photocatalytic hydrogen evolution. The pristine hydrangea-like TiO 2 support shows a promising performance of hydrogen evolution (1.8 mmol·h −1 ·g −1 ), which is ~ 10.7 times higher than that of the commercial P25 (168 μmol·h −1 ·g −1 ). After ultra-fine Cu clusters decoration, a maximal hydrogen evolution performance (3.7 mmol·h −1 ·g −1 ) is achieved in the optimized system 6Cu–TiO 2 (6 wt%). Experimental and theoretical studies demonstrate that the ultra-fine Cu clusters decoration could promote the charge separation and transfer process effectively. The Cu clusters also act as reaction sites for reduction of H 2 O to H 2 . These results are of great importance for the study of Cu-based co-catalyst systems and also shed light on the development of other non-noble metal co-catalysts in photocatalysis hydrogen evolution. Graphical abstract
研究领域:
材料科学
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能源科学
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产品关联
DOI
高影响因子
INORGANICA CHIMICA ACTA
·
2022
·
IF 3.118
Jing-Wen Zhang,Ling-Xiao Wang,Xun Cheng,Lin-Lin Hou,Jing-Zhe Li,Chun-Feng Wang,Xiao-Wei Yan,Kuan-Guan Liu
To prepare new series of mixed-valence polynuclear Cu(I/II) clusters, chloride ions are introduced to construct two mixed-valence polynuclear Cu(I/II) clusters for evaluating their photothermal conversion performance. X-ray single-crystal structural analysis reveals their molecular formula are {Cu II [Cu I (Cy 3 P)] 4 (BTA) 4 Cl 2 }·5DMF (I·5DMF, Cy 3 P = triscyclohexylphosphine, BTA = benzotriazole, DMF = N, N -Dimethylformamide) and {(Cu II ) 3 [Cu I (PPh 2 Py)] 6 (BTA) 8 Cl 4 }·6DMF (II· 6 DMF, Ph 2 PyP = diphenyl-2-pyridylphosphine), respectively. X-ray Photoelectron Spectroscopy (XPS) and Electrospray Ionization Mass Spectrometry (ESI-MS) confirm their chemical composition and charge state. The reported two mixed-valence Cu I /Cu II clusters have different nucleus (penta-nucleus for I and nano-nucleus for II) and different proportion of valence state (1/4 for I vs 1/2 for II). The thermogravimetric analysis (TGA) reveals the thermal stability of both clusters is less than our previously reported penta-nucleus mixed-valence Cu I /Cu II clusters. Contrastively studies of their optical absorption properties by the solid-state ultraviolet diffuse reflection spectra indicate high-nucleus mixed-valence Cu I /Cu II cluster with higher proportion of Cu II is superior to those penta-nucleus mixed-valent Cu(I/II) clusters. With the introduction of chloride ions to the structures of mixed-valence Cu I /Cu II clusters have not remarkably changed their photothermal conversion performance. This study provides a practicable way to construct new mixed-valence Cu I /Cu II clusters with different photothermal conversion performance.
研究领域:
化学
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材料科学
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DOI
高影响因子
ChemSusChem
·
2021
·Vol. 15
·期 1
·e202102010
·
IF 8.928
Han Zhang,Yu Yang,Yongxiang Liang,Jun Li,An Zhang,Han Zheng,Zhigang Geng,Fengwang Li,Jie Zeng
Graphical Lend me your EORs : Electrochemical oxidation-reduction (EOR) processing of a Cu-based metal-organic framework results in the formation of sub-nanometer Cu clusters that retains the organic linkers for highly selective and durable electrosynthesis of methane from the electrochemical CO 2 reduction reaction. Electrochemical CO 2 methanation powered by renewable electricity provides a promising approach to utilizing CO 2 in the form of a high-energy-density, clean fuel. Cu nanoclusters have been predicted by theoretical calculations to improve methane selectivity. Direct electrochemical reduction of Cu-based metal-organic frameworks (MOFs) results in large-size Cu nanoparticles which favor multi-carbon products. This study concerns an electrochemical oxidation-reduction method to prepare Cu clusters from MOFs. The derived Cu clusters exhibit a faradaic efficiency of 51.2 % for CH 4 with a partial current density of >150 mA cm −2 . High-resolution microscopy, in situ X-ray absorption spectroscopy, in situ Raman spectroscopy, and a range of ex situ spectroscopies indicate that the distinctive CH 4 selectivity is due to the sub-nanometer size of the derived materials, as well as stabilization of the clusters by residual ligands of the pristine MOF. This work offers a new insight into steering product selectivity of Cu by an electrochemical processing method.
研究领域:
化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2023
·Vol. 33
·期 16
·2214215
·
IF 19
Xiaosong Hu,Xinyu Liu,Xin Hu,Chaoyue Zhao,Qingxin Guan,Wei Li
Reverse water-gas shift (RWGS) reaction is the initial and necessary step of CO 2 hydrogenation to high value-added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnN x @C-N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four-coordinate Zn-N 4 sites and low valence CuN x clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn-N 4 and N 4 structures, which show strong Lewis basicity and has strong adsorption for *CO 2 and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO 2 conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO 2 conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu-ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO 2 . In the catalytic process, CuN x not only adsorbs and activates H 2 , but also cooperates with the adjacent Zn-N 4 and N 4 structures to jointly activate CO 2 molecules and further promotes the hydrogenation of CO 2 . This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts.
研究领域:
化学
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Yuying Zhao,Shengchun Hu,Qixin Yuan,Ao Wang,Kang Sun,Ziyun Wang,Mengmeng Fan,Jianchun Jiang
Electrochemical CO 2 conversion into formate by intermittent renewable electricity, presents a captivating prospect for both the storage of renewable electrical energy and the utilization of emitted CO 2 . Typically, Cu-based catalysts in CO 2 reduction reactions favor the production of CO and other by-products. However, we have shifted this selectivity by incorporating B, N co-doped carbon (BNC) in the fabrication of Cu clusters. These Cu clusters are regulated with B, N atoms in a porous carbon matrix (Cu/BN-C), and Zn 2+ ions were added to achieve Cu clusters with the diameter size of ∼1.0 nm. The obtained Cu/BN-C possesses a significantly improved catalytic performance in CO 2 reduction to formate with a Faradaic efficiency (FE) of up to 70 % and partial current density (j formate ) surpassing 20.8 mA cm −2 at −1.0 V vs RHE. The high FE and j formate are maintained over a 12-hour. The overall catalytic performance of Cu/BN-C outperforms those of the other investigated catalysts. Based on the density functional theory (DFT) calculation, the exceptional catalytic behavior is attributed to the synergistic effect between Cu clusters and N, B atoms by modulating the electronic structure and enhancing the charge transfer properties, which promoted a preferential adsorption of HCOO* over COOH*, favoring formate formation.
研究领域:
材料科学
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电化学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2025
·
IF 5.4
Hui Chen,Chuhua Qi,Sijing Zhang,Yuanzhen Zhou
Developing efficient and sustainable photocatalysts for reducing toxic chromium (VI) is paramount in environmental remediation. The atomic-level integration of redox-active copper clusters into crystalline covalent organic frameworks (COFs) presents a transformative approach for designing high-performance environmental photocatalysts. In this work, we demonstrate the successful construction of copper(I) cluster-incorporated MCOFs as high-performance redox-active photocatalysts for the solar-driven reduction of chromium(VI) contaminants. This innovative design synergistically combines the photoredox capabilities of Cu(I) clusters with the structural advantages of MCOFs, thereby achieving exceptional photocatalytic efficiency in chromium(VI) detoxification. The prepared Cu(I) cluster-based MCOFs possess high crystallinity, permanent porosity, outstanding stability, and promising photoredox properties. Under visible light irradiation, the Cu(I) cluster-based MCOFs exhibit exceptional photocatalytic activity with fast rate and efficient removal, after 1 hour of visible light irradiation, all Cu(I) cluster-based MCOFs show significant photocatalytic activity for the reduction of Cr(VI) to Cr(III) with the conversion rate exceeding 99 %. After five recycling, no significant decline in the photocatalytic efficiency was observed. Detailed spectroscopic and electrochemical studies elucidated that Cu(I) clusters play a crucial role in the photocatalytic process. This work provides valuable insights into the design and development of novel metal covalent organic frameworks for environmental remediation applications. The structure-activity relationships revealed herein (e.g., conduction band modulation through ligand electronic effects) offer rational design principles applicable to broader environmental and energy applications.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2025
·
IF 3.7
Zheng Liu,Jun-Jie Fang,Zhi-Yi Wang,Yun-Peng Xie,Xing Lu
Graphical The inclusion of carboxylic acid ligands significantly impacts the structural arrangement of the metal core in Cu(I) alkynyl clusters, thereby affecting their fluorescence properties. Furthermore, the incorporation of ferrocene into these clusters has been noted to induce modifications in the electrochemical performance of the Cu(I) alkynyl clusters. Surface ligands play a pivotal role in the functional design of atomically precise Cu(I) nanoclusters. They act as protective agents, ensuring the stability of the Cu(I) clusters, while also influencing their structure and properties. This study delves into the synthesis, structure, and properties of innovative Cu(I) nanoclusters co-stabilized by carboxylic acid and alkynyl ligands. The findings reveal that these surface ligands wield a significant impact on the cluster's structure and can even modulate the luminescent characteristics of the Cu(I) alkynyl clusters. Moreover, density-functional theory (DFT) calculations shed light on how different carboxylic acid ligands affect the UV-visible absorptivity of paired Cu(I) clusters. In addition, ferrocene carboxylic acids were employed as protective ligands to impart electrochemical properties to the Cu(I) clusters. This research presents an effective methodology for synthesizing atomically precise Cu(I) clusters shielded by carboxylic acid ligands.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Bingyan Han,Yajun Chen,Qingdong Liu,Yuncong Gao,Jiao Wang,Haiyan Liu,Gaohong He
Aggregation-induced emission enhancement is one of the main methods for designing copper clusters (CuNCs) with high fluorescence intensity. In this study, H 2 O can rapidly construct stable hydrogen bonds with 2-thiobarbituric acid ligands of CuNCs, leading to denser aggregation between CuNCs. This process can occur at a level of intensity visible to the naked eye and can be completed within 30 s. As a result, the fluorescence turns to yellow with emission wavelength at 573 nm from red with emission wavelength at 638 nm, and the quantum yield has been increased to 50.03 %. The noticeable “turn on” phenomenon can be utilized for detecting alcohol content in low-alcohol liquor quality control. Additionally, bright luminous make Y-CuNCs can be employed for accurate identification of human latent fingerprints (LFPs), which can accurately identify the third level structure of the LFPs.
研究领域:
化学
·
材料科学
·
分析化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Meng Liu,Caixia Miao,Peng Xiao,Zhijie Wu
The direct conversion of methanol, a cheap and readily available feedstock, into value-added methyl acetate (MA) is a promising route. Considering the MA formation mechanism is complex, the design of highly selective catalysts is a huge challenge. Herein, we report a Cu@Zr-Beta catalyst, encapsulated Cu metal clusters within Zr-Beta zeolite by an in-situ two-step hydrothermal method, which exhibits high dispersion of Cu species and strong metal-support interaction between Cu and framework Zr species. The formation rate of MA using the Cu@Zr-Beta catalyst is as high as 2.84 mol kg cat -1 h −1 with a methanol conversion of 8.7 % and a MA selectivity of 55.8 % at 240 °C, which outperforms comparison catalysts. Experimental and characterization studies confirm that the electronic interactions between the encapsulated Cu species and Zr atoms not only enable the production of abundant and stable Cu + species but also promote the synergistic effect between Cu + and framework Zr species, thus accelerating the conversion of methanol to MA. In-situ FT-IR and reaction results show that the Cu 0 site is responsible for the dehydrogenation of methanol to CH 2 O*, which then moves to Cu + -Zr(OSi) 4 site and couples with CH 3 O* to form CH 3 CHO*, and finally produces MA through C-O coupling with another CH 3 O*.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
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