GREEN CHEMISTRY
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2022
·Vol. 24
·期 22
·8840-8852
·
IF 11.034
Zongyang Liu,Yuan Tan,Jie Li,Xiuli Li,Yan Xiao,Juan Su,Xingkun Chen,Botao Qiao,Yunjie Ding
Aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a promising alternative route to produce renewable biodegradable plastics, which has stimulated intense interest in recent years. Supported gold catalysts have shown great potential for this reaction, but the selectivity and stability need to be improved. In addition, the requirement for base additives makes the process less effective and sustainable. Herein, highly active and selective Au–Ag bimetallic nanoclusters supported on MgAl-hydrotalcite (HT) were developed for HMF oxidation to FDCA under base-free reaction conditions using molecular oxygen as the oxidant. The presence of small amounts of Ag (0.034–0.065 wt%) in Au25 clusters greatly enhanced the catalytic reaction rates and selectivity for HMF tandem oxidative steps, leading to both high conversion of HMF (>97%) and high yield of FDCA (>95%). Besides, the catalyst stability was also enhanced by the addition of Ag. The characterization results suggested that the substitution of Ag atoms modified the electronic structure of Au while likely maintaining the primary geometry. Thus, a significant synergistic effect could be observed over trace Ag modified Au–Ag bimetallic nanoclusters. The present work provides new insight into the alloying effect, and helps understand highly efficient Au-based catalysts for aerobic oxidation of biomass derived molecules under base-free conditions.
研究领域:
催化化学
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可再生资源化学
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DOI
高影响因子
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
·
2021
·Vol. 22
·期 16
·8668
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IF 5.924
Jie Li,Shiyi Wang,Huayin Li,Yuan Tan,Yunjie Ding
The synthesis of ester compounds is one of the most important chemical processes. In this work, Zn-Mg-Al mixed oxides with different Zn2+/Mg2+molar ratios were prepared via co-precipitation method and supported gold nanoclusters to study the direct oxidative esterification of aldehyde and alcohol in the presence of molecular oxygen. Various characterization techniques such as N2-physical adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and CO2temperature programmed desorption (TPD) were utilized to analyze the structural and electronic properties. Based on the results, the presence of small amounts of Zn2+ions (~5 wt.%) provoked a remarkable modification of the binary Mg-Al system, which enhanced the interaction between gold with the support and reduced the particle size of gold. For oxidative esterification reaction, the Au25/Zn0.05MgAl-400 catalyst showed the best performance, with the highest turnover frequency (TOF) of 1933 h−1. The active center was believed to be located at the interface between metallic gold with the support, where basic sites contribute a lot to transformation of the substrate.Keywords:gold catalyst;cluster;hydrotalcite;oxidative esterification;methyl isobutyrate
研究领域:
化学工程
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催化材料
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DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2020
·
IF 4.825
Wan Jiang,Yuyuan Bai,Qinzhen Li,Xiean Yao,Hui Zhang,Yongbo Song,Xiangming Meng,Haizhu Yu,Manzhou Zhu
An understanding of the response of nanomaterials to specific environmental parameters is an essential prerequisite for their practical use, especially in living systems. Herein, we disclose the preparation of a water-soluble nanocluster Au16(SR)12 (SR denotes deprotonated captopril) and its characterization by a combination of theoretical (e.g., density functional theory calculations) and experimental (UV–vis, electrospray ionization mass spectrometry, etc.) methods. Interestingly, Au16(SR)12 was found to convert to Au18(SR)14 under acidic conditions, while the reverse conversion from Au18(SR)14 to Au16(SR)12 occurred upon the addition of base. A mechanistic investigation determined this pH regulation to originate from the distinct steric and electrostatic properties of these two clusters. This study is the first to report the susceptibility of Au18(SR)14 and Au16(SR)12 to pH, and the distinct pH stability unambiguously reveals the importance of size-tracking of nanomaterials in living systems for future clinical applications.
研究领域:
纳米材料
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生物化学
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理论计算
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DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Yongqi Yang,Jiaqi Li,Xinyao Li,Lin Guan,Zijian Gao,Lijie Duan,Fei Jia,Guanghui Gao
Paper, for writing and printing, is consumed a lot in modern life. However, the production of conventional paper could cause many problems, such as deforestation and environmental pollution. Therefore, it is necessary and urgent to explore novel strategies to solve these problems. In this work, a polyoxometalate-doped gelatin film with high strength, excellent transparency, and fast photochromic properties is designed and prepared. The film can display different colors by using a variety of reagents, exhibiting its potential application as a paper medium. Its rapid photochromic properties allow complex high-resolution images to be displayed by UV light printing. It is found that the mechanical and photochromic properties could be regulated by the introduction of triethylene glycol, and the fading process could be controlled by changing the temperature and humidity. Moreover, it is rewritable, self-repairable, and recyclable, and can also achieve long-term preservation without fading. It is envisioned that the environmentally friendly films with low cost, ease of preparation, and recycling advantages have the potential to be an alternative to conventional paper for writing and printing.
研究领域:
材料科学
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环境科学
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DOI
PubMed
高影响因子
CHEMICAL PAPERS
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2022
·Vol. 76
·期 12
·7855-7863
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IF 2.146
Zhang Shen,Jin Mei-ling,Gao Ya-xi,Li Wen-qin,Wang Xin-yu,Li Xin-xin,Qiao Jia-qi,Peng Yang
Herein, histidine, as a protective agent, was applied for the synthesis of copper nanoclusters (histidine-Cu NCs) by using ascorbic acid as an efficient reducing agent. The as-fabricated fluorescent histidine-Cu NCs displayed blue-green emission wavelength at 492 nm with the excitation of 410 nm. Using histidine-Cu NCs as a novel nanoprobe, the fluorescent “turn-off” mechanism was developed for the determination of furaltadone accompanying linear attenuation of fluorescence at 492 nm. Furaltadone acted as a quencher and ln ( F 0 / F ) value of histidine-Cu NCs had an excellent linear relationship of furaltadone concentrations (0.5–500 μM) (the F 0 and F are referred to the fluorescence intensity of probe without and with furaltadone), along with the detection limit and linear fit constant of 0.085 μM and 0.9948, respectively. The fluorescence quenching of histidine-Cu NCs demonstrated good selectivity for furaltadone over other potential control substances. The quenching mechanism might be assumed to be static quenching. This system was proved to be an appropriate detection pattern for furaltadone sensing in real medical samples.
研究领域:
分析化学
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生物医学工程
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DOI
高影响因子
Journal of Materials Chemistry A
·
2025
·
IF 9.5
Yunxiang Zhang,Zhichao Mu,Chenliang Zhou,Hazem Abdelsalam,Xingmeng Zhou,Lin Shi,Zhili Chen,Yiran Liang,Zhongjie Wang,Qinfang Zhang
Bi-based Sillén–Aurivillius oxyhalides have attracted extensive attention from researchers owning to their wide range of light absorption, appropriate band structure, and excellent stability; however, their practical application is still limited by their rapid charge recombination. Herein, silver (Ag)-cluster-decorated novel Sillén–Aurivillius oxyhalides (bismuth iron titanium oxyhalide (Bi7Fe2Ti2O17Cl)) with abundant oxygen vacancies (OVs), were successfully synthesized to achieve efficient light absorption and interfacial charge separation. The optimal Ag/Bi7Fe2Ti2O17Cl composites showed excellent tetracycline hydrochloride (TCH) degradation and CO2 reduction efficiencies. The theoretical and experimental results demonstrate that the superior activity is primarily due to the increased magnetic moment of Bi7Fe2Ti2O17Cl induced by the interactions between Ag and O atoms, which strengthens the built-in electric field at the Schottky junction interface and promotes the transfer of photogenerated electrons from Ag clusters to oxyhalides, thus enhancing the generation of charge carriers in the semiconductor and inhibiting bulk recombination. Simultaneously, the synergistic effects of the thermodynamics and kinetics of photocatalytic CO2 reaction along with a lower Gibbs free energy are also responsible for the outstanding CO generation process. This work emphasizes the promising role of metal clusters as co-catalysts in the field of photocatalysis.
研究领域:
材料科学
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环境科学
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DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-13
·
IF 15.7
Xu Guangyuan,Peng Xingjie,Wu Chuanqiang,Xi Shibo,Xiang Huixin,Feng Lei,Liu Zhendong,Duan Yi,Gan Lijin,Chen Si,Kong Yuan,Ma Yanzhe,Nie Fujing,Zhao Jie,Hai Xiao,Wei Wei,Zhou Meng,Wang Tianfu,Yao Chuanhao,Zhou Wu,Yan Huan
CO 2 electroreduction to CO promises to give an efficient strategy for CO 2 fixation and transformation. However, current reported active sites fail to deliver sufficient activity with high CO Faradic efficiency (FEco) over a wide range of potential. Here, we show a general synthetic protocol to fabricate a batch of highly pure and active NiN 2 catalysts with precise engineering of the uniform-large ( UL ) vacancy around the active sites, which is accomplished through the ‘pre-deposition + pyrolysis’ of various atomically precise Ni clusters (Ni n ) and in-situ etching of the support by the ‘nano bomb’ (sulfur-ligand in the clusters). The NiN 2 sites with UL vacancies could achieve a high turnover frequency (TOF) of 350000 h −1 with ~100% FEco in a wide potential range of 1500 mV. In-situ infrared spectra and theoretical calculations reveal that a highly pure NiN 2 site with UL vacancy contributes to this remarkable catalytic performance compared to the counterparts. This general synthetic strategy enables us to simultaneously engineer active sites and surrounding vacancies with the employment of atomically precise metal clusters, thereby enhancing catalytic performance for other specific reactions.
研究领域:
材料科学
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电化学
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催化反应
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产品关联
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
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环境科学
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电化学
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DOI
高影响因子
MICROCHIMICA ACTA
·
2020
·Vol. 187
·期 6
·1-9
·
IF 6.232
Li Wanying,Qian Hui,Liu Rui,Zhao Xiaoli,Tang Zhi,Huang Xianhuai,Li Weihua,Chen Xiaoming,Xie Fazhi,Zou Wensheng,Qu Qishu
Based on a detailed study of the hydrolysis process of tetrabutyl orthotitanate (TBOT), TiO 2 nanoclusters were modified inside the pores of SiO 2 core-shell particles instead of the outside. The pore size distribution of SiO 2 core-shell spheres modified with TiO 2 (SiO 2 @ d SiO 2 @TiO 2 ) was analyzed by Barrett-Joyner-Halenda (BJH) method and density functional theory (DFT) method, respectively. The results of the DFT calculations demonstrate that the TiO 2 nanoclusters are always first formed in bulk solution and then enter the pores. By regulating the rate of hydrolysis of TBOT, almost all of the TiO 2 nanoclusters are modified into the pores and the structure of the original SiO 2 core-shell sphere is hardly affected. The morphology of the particles was characterized by scanning electron microscopy and transmission electron microscopy. The crystal phase of TiO 2 was measured by XRD. SiO 2 @ d SiO 2 @TiO 2 spheres functionalized with C18 were packed into a stainless steel column. The chemical stability of SiO 2 @ d SiO 2 @TiO 2 spheres under alkaline was tested by flushing of a mobile phase at pH 13 for 7 days. The efficiency of the column after the alkali solution treatment still reaches 98,430 plates m −1 , which is only about 1.6% lower than that before the alkali solution treatment. A series of basic and acidic analytes were also separated on the column.
TiO 2 nanocrystals were coated into the pore of core-shell silica spheres. The prepared particles were packed into the column and separation performance up to 98,430 plates per meter was achieved.
研究领域:
材料科学
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分析化学
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产品关联
DOI
PubMed
高影响因子
Chem
·
2024
·
IF 19.1
Ying-Xue Yuan,Jia-Ni Zhang,Jun-Ru Wang,Kai Li,Shuang-Quan Zang
The construction of effective artificial chiral light-harvesting systems ( C -LHSs) is significantly important as it provides insights into the hierarchical levels of chirality evolution in natural systems. Herein, we devised pairs of chiral blue emitters, S -/ R -binaphthalene dioxygen- N -octadecamidephthalimide ( S -/ R -BPOA), which function as donors of chirality and light absorbers. S -/ R -BPOA co-assembled with enantiomers of atomically precise yellow-emitting subnanometer-scale Ag 6 clusters to fabricate C -LHSs. Within these hybrid C -LHSs, we successfully resolved enantioselective chirality/energy transfer that was dependent on the handedness of the components. This promoted the efficient circularly polarized energy transfer in chirality-compatible ensembles, resulting in a remarkable amplification of circularly polarized luminescence (CPL) in the ultrasmall silver cluster. The achieved dissymmetry factor ( g lum ) reached an impressive value of 1.54 × 10 −2 , and white-light CPL with chromaticity coordinates of (0.32, 0.33) was obtained. Furthermore, the customizable fluorescence and CPL in these C -LHSs bestow them with potential application possibilities in information storage and encryption.
研究领域:
材料科学
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光学
·
化学
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DOI
高影响因子
TALANTA
·
2024
·
IF 5.6
Na Li,Qing-Hong Long,Xin-Yuan Li,Can Dong,Tian-Sheng Zhao,Xi Mai,Yong-Sen Zhao,Zhong-Feng Gao,Qin Wei,Fan Xia
Understanding charge transport in metal ion-mediated glutathione-stabilized gold nanoclusters (GSH-Au NCs) has proved difficult due to the presence of various competitive mechanisms, such as electron transfer (ET) and aggregation induction effect (AIE). In this paper, we present a dual-channel fluorescence (FL) and second-order Rayleigh scattering (SRS) sensing method for high-throughput classification of metal ions, relying on the competition between ET and AIE using GSH-Au NCs. The SRS signals show significant enhancement when Pb 2+ , Ag + , Al 3+ , Cu 2+ , Fe 3+ , and Hg 2+ are present, as a result of the aggregation of GSH-Au NCs. Notably, the fluorescence signal exhibits the opposite trend. The FL intensities of GSH-Au NCs are enhanced by Pb 2+ , Ag + , and Al 3+ through the AIE mechanism, while they are quenched by Cu 2+ , Fe 3+ , and Hg 2+ , which is dominated by the ET mechanism. By employing principal component analysis and hierarchical cluster analysis, these signals are transformed into unique fingerprints and Euclidean distances, respectively, enabling successful distinction of six metal ions and their mixtures with a low detection limit of 30 nM. This new strategy has successfully addressed interference from impurities in the testing of real water samples, demonstrating its strong ability to detect multiple metal ions. Impressively, we have achieved molecular cryptosteganography, which involves encoding, storing, and concealing information by transforming the selective response of GSH-Au NCs to binary strings. This research is anticipated to advance utilization of nanomaterials in logic sensing and information safety, bridging the gap between molecular sensors and information systems.
研究领域:
分析化学
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纳米科学
·
信息加密
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产品关联
DOI
PubMed
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2025
·
IF 5.4
Yu Chen,Huan Chen,Haihua Wang,Xia Xin,Wenbing Kang
Silver nanoclusters (NCs) possess precise and tunable structures characterized by their unique properties, yet a single component often underperforms in practical applications. In this work, a series of stable and highly effective antibacterial gels were prepared by incorporating fluoropolymer (perfluoro-2, 5-dimethyl-3, 6-dioxactyl glycol acrylate-co-acrylic acid, FAA) into aqueous solutions of (NH 4 ) 6 [Ag 6 (mna) 6 ] (Ag 6 -NCs). It can be quickly gelated within a few seconds to achieve the rapid transformation of one-dimensional into three-dimensional structures. These gels are formed through the layering of nanowires, and their mechanical properties can be tailored by adjusting the FAA concentration. The assembly process of Ag 6 -NCs/FAA hydrogels was investigated by comparing it with various poly carboxylic acids, neutralized FAA, and aqueous AgNO 3 solutions under identical experimental conditions. This assembly results from various interactions, including hydrophobic interactions, van der Waals forces and hydrogen bonds. Furthermore, the hydrogel system demonstrated improved antibacterial activity due to the presence of Ag ions and fluorine atoms. The functional composite of materials, achieved through heterogeneous assembly, promoted the design of metal NC materials and furthered the development of macro manufacturing technology.
研究领域:
材料科学
·
生物学
·
化学工程
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）