JOURNAL OF MOLECULAR STRUCTURE
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2025
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IF 4.7
Yu-Teng Zhang,Jing- Yu Sun,Jian Li,De-Sheng Wei,Wan-Yi Lan,Nan Lv,Shuang-Bao Li
This study reports one-pot microwave-assisted solvothermal synthesis of Ti-Zr bimetallic organic cages (TiZrT-BTC-α, where α denotes the actual Ti molar percentage and T represents the tetrahedral cage structure). The reaction employed zirconocene dichloride (Cp 2 ZrCl 2 , Cp = η 5 -C 5 H 5 ), titanocene dichloride (Cp 2 TiCl 2 ) and 1,3,5-benzenetricarboxylic acid (H 3 BTC) as solid precursors to form a V 4 F 4 (V = vertex and F = face) coordination tetrahedron. The presence of the characteristic Ti-O vibration band at 420 cm -1 in the FT-IR spectrum, along with the characteristic Ti 4+ band signal at 458.6 eV in the XPS spectrum, collectively demonstrates the successful incorporation of titanium into the molecular cage structure. Notably, the introduction of titanium endowed the material with visible light absorption capability and modulates its electronic structure, reducing the band gap value from 3.73 eV (ZrT-BTC) to 2.48 eV (TiZrT-BTC-7.9). The photocatalytic activities of TiZrT-BTC-α were evaluated using tetracycline hydrochloride (TC) as a target pollutant under visible light illumination. Among the series, TiZrT-BTC-7.9 demonstrated excellent photocatalytic activity, achieving 92.17% degradation efficiency for TC (20 mg/L) within 3 hours. Electron spin resonance (ESR) spectroscopy combined with radical trapping experiments identified superoxide radicals (·O 2 - ) served as the dominant reactive species. This work paves the way for developing cage-based photocatalysts with tunable optoelectronic properties.
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ChemNanoMat
·
2025
·
IF 2.6
Muhammad Kashif Majeed,Arshad Hussain,Muhammad Akram,M.Umar Majeed,Muhammad Arshad,Adil Saleem,Rashid Iqbal
The precise manipulation of pore structure, organic linkers, and disposition of active and co-active sites in metal-organic frameworks (MOFs)-based materials allows for the design of materials with tailored catalytic properties. However, studies that address their kinetic, dynamic, and mechanistic roles in target reactions are scarce. The development of a new functionalization method to introduce acidity into MOFs is established for heterogeneous catalysis. Exploring the effect of ligand functionalization in MOF type UiO-66(Zr) impacts its ability to catalyze the dimerization reaction of cyclohexanone. Upon treatment with a series of linkers and the addition of HCl, chemically stable MOF structures such as UiO-66 can be protonated, resulting in an acidic group attached to aromatic terephthalate linkers in the structure. A general synthetic strategy has been developed to produce functionalized UiO-66-FG compounds [FG = NH2, NO2, Br, OH, and (OH)2]. The functionalized acidic frameworks present enhanced catalytic activity toward the self-condensation of cyclohexanone. Investigating these aspects can provide valuable insights into how the functionalization of MOFs performs in real-world self-condensation scenarios and help in optimizing their practical applications.
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JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
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2025
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IF 3.1
Li Kaiqian,Zhang Xupeng,Li Xianghong,Chang Qiaowen,Deng Shuduan,Zhu Gang
Introducing novel bimetallic metal–organic frameworks (Cu/Zr-MOF) into wood cellulose scaffolds via an in situ growth strategy represents an effective approach to enhance the fire retardancy of wooden products. This work evaluates the effects of Cu/Zr-MOF loading content embedded in wood composite on the MOF morphology and flame retardancy of natural wood (NW). We discovered that MOF loading has a significant impact on the morphology of Cu/Zr-MOF. Specifically, with an increase in the amount of MOF precursors, the morphological transformation is from spherical to regular octahedra. Furthermore, the incorporation of high MOF loading remarkably enhanced the thermal stability at the early stage and exhibited significantly improved residual content. With 24 mass% loading of Cu/Zr bimetallic MOF, the highly flame-retardant wood composite (Cu-U-W-3) was obtained. Compared to pure NW, the peak heat release rate (pHRR) and total heat release (THR) were reduced to 25.25 W g −1 and 5.0 kJ g −1 , respectively. The limiting oxygen index (LOI) of the treated sample reached 24.81%, showing outstanding self-extinguishing ability. According to the char residue analysis, it was found that Cu-Zr bimetallic MOF anchored on the cell wall exhibited catalytic carbon-forming effect, thereby facilitating the generation of high-quality residual char. The enhanced fire safety of natural wood can be attributed to the oxygen barrier and the reduced heat transfer characteristics of the dense carbon layer. This work presents a novel methodology for the fabrication of bimetallic MOF hybrid flame retardants, with the objective of enhancing the flame retardancy of wooden products.
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WATER AIR AND SOIL POLLUTION
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2025
·Vol. 236
·期 8
·1-19
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IF 3
Ou Qianhui,Xiong Yan,Chen Li,He Deyong,Zhou Chuxiang,Wang Lan
The nanocomposite materials are highly promising candidates for adsorption applications in dyed wastewater due to their distinctive structural properties. In this work, the nanocomposite hybrids of UiO-66@GO were first synthesized by specifically anchoring Zr-based metal organic framework (MOF) of UiO-66 onto graphene oxide (GO) nanolayer through solvothermal method. Then the composite matrix microspheres (CMMs) of UiO-66@GO were subsequently prepared by embedding the obtained UiO-66@GO nanocomposite into sodium alginate (SA) microspheres through self-assembly cross-linking process. Finally, the prepared UiO-66@GO CMMs were applied for the adsorption of organic dye pollutant and showed efficient water purification performance. As a result, the UiO-66@GO CMMs exhibited selective cationic dye adsorption for Rhodamine B (RhB + ). The experimental results revealed that the adsorption kinetics followed by the pseudo-second-order (PSD) model with rate constant k 2 = 0.95 × 10 –3 g mg −1 min −1 , and the thermodynamics followed by the Langmuir model with adsorption capacity of 345.66 mg mg −1 . Notably, the UiO-66@GO CMMs demonstrated excellent adsorption removal of a significant removal efficiency of 98% towards 10 ppm Rh-B and a rapid adsorption response time of ~ 5 min. Meanwhile, the UiO-66@GO CMMs maintained long-term stability with adsorption efficiency > 95% over 30 days and effective reuse with resorption efficiency > 90% using DMF-H₂O as eluent. In this study, SA has served as a porous supporting matrix to immobilize UIO-66@GO nanoparticles, having mitigated issues of aggregation and leaching common to nanoscale adsorbents while improving reusability. The synergistic effect between UIO-66 and GO has further enhanced pollutant adsorption capacity, demonstrating significant potential for dye wastewater treatment applications.
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CHEMICAL PAPERS
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2025
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IF 2.5
Zhao Chun-Yan,Hu Xiu-Li,Zhou Wei
Calcium looping represents a high-temperature method designed to capture CO 2 , making it appropriate for CO 2 capture from flue gases post-combustion in power plants after combustion or for integration with fuel transformation techniques in pre-combustion CO 2 sequestration systems. This method employs solid sorbents of CaO sourced from natural limestone, leveraging the chemical interaction of CaO with CO 2 , which ultimately results in the formation of CaCO 3 , thereby facilitating effective CO 2 capture. In this research, multiple metal-incorporated CaO-based sorbents were produced through the sol–gel method. Notably, the CaO-based sorbent with a Ca/Ce doping ratio of 15 demonstrates exceptional CO 2 capture ability and stability, maintaining 13.20 mmol/g of CO 2 adsorption capacity after 20 carbonation/calcination cycles. Various characterization techniques, including X-ray diffraction (XRD), N 2 physisorption, scanning electron microscopy (SEM), high-angle annular dark field scanning transmission electron microscopy/energy dispersive spectroscopy (HAADF-STEM/EDS), temperature-programmed-desorption with CO 2 (CO 2 -TPD), Fourier Transform Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) are employed to demonstrate that the presence of nanoscale CeO 2 significantly enhanced the diffusion of CO 2 during the adsorption process.
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Materials
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2025
·Vol. 18
·期 9
·1988
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IF 3.2
Yushi Qi,Fangming Wei,Yu Wang,Yu Jin,Xusheng Chang,Gang Chen
To enhance the mechanical properties of 6082 aluminum alloy, a novel Sc- and Zr-microalloyed 6082 alloy was fabricated through squeeze casting technology. Microalloying with Sc and Zr substantially refined the microstructure of alloy, achieving an average grain size of 136.36 μm—a 31.7% reduction compared to the baseline 6082 alloy. Furthermore, the addition of Sc and Zr effectively refined the coarse AlFeMnSi intermetallic phases, mitigating their inherent brittleness. The Sc/Zr-modified alloy exhibited delayed age-hardening kinetics, requiring 100% longer aging time to reach peak hardness due to Sc/Zr-induced retardation of β’’-phase precipitation. The optimized alloy demonstrated better mechanical properties, showing 10.4%, 8.0%, and 71.8% enhancements in yield strength, ultimate tensile strength, and elongation, respectively, over the non-microalloyed counterpart. The squeeze-cast Sc/Zr-modified alloy valve body showed yield strength exceeding 300 MPa and elongation above 10% across various sections, which verifies the effectiveness of this integrated microalloying and forming approach.
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高影响因子
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
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2025
·Vol. 36
·期 12
·1-10
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IF 2.8
Hao Yi,Ma Tianzhu,Yan Yangxi,Li Zhimin,Murakami Ri-ichi,Zhang Dongyan
Nickel-rich cobalt-free cathode materials have received widespread attention due to their advantages of high energy density, low-cost, and environmental friendliness. However, the instability of the structure and surface interface accelerates the capacity degradation of these materials during cycling. Here, we synthesized LiNi 0.9 Mn 0.1 O 2 (NM91) nickel-rich cobalt-free cathode material by sol–gel method and optimized it by Zr doping to enhance the electrochemical performance. Comprehensive structural characterization confirmed that Zr doping effectively suppressed the volume change and microcrack formation during the H2–H3 phase transition, reduced the side reactions occurring on the surface, and generated a thinner and more stable CEI layer, which effectively prevented the erosion of the electrolyte. As a result, Zr–NM exhibits superior cycling stability and rate performance. Notably, 0.75%Zr–NM shows excellent capacity retention of 92.36% at 1 C and achieves a discharge specific capacity of 138 mAh·g −1 even at a high current density of 10 C.
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Journal of Environmental Chemical Engineering
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2025
·
IF 7.2
Fangfang Li,Xiaofang Hou,Wei Fu,Jinjin Wang,Ying-Hua Zhou
The efficient transformation of CO 2 into high-value chemicals remains a significant challenge, particularly in the design of heterocatalysts capable of simultaneous multi-site activation towards the substrate. In this work, we develop the novel Zr-MOF catalysts incorporating both cobalt(II) meso-tetra(4-carboxyphenyl)porphine (CoTCPP) complex and the imidazolium bromide-based ionic liquid (IL) containing different alkyl chain (RImBr), where R = Et, Pr, Bu, and Pe), denoted as CoTCPP-UiO-66-IL(RImBr). The catalysts were synthesized through a solvothermal method followed by a post-synthetic modification. Among the prepared catalysts, CoTCPP-UiO-66-IL(BuImBr) demonstrated exceptional performance on the solventless and cocatalyst-free conversion of epichlorohydrin into chloropropene carbonate, achieving a remarkable 99% yield under mild conditions (90 °C and 1.0 bar CO 2 ). This outstanding catalytic efficiency was attributed to the synergistic effects of the dual Lewis-acid active sites offered by Zr-MOF node and the integrated CoTCPP complex, the strong nucleophilicity resulting from the incorporated imidazolium bromide-type IL, and the improved CO 2 adsorption capacity. Additionally, the CoTCPP-UiO-66-IL(BuImBr) catalyst exhibited excellent recyclability and broad substrate versatility in epoxide cycloaddition. These findings provide valuable insights into the development of multifunctional MOF-based heterogeneous catalysts with high activity and sustainability for CO 2 conversion applications.
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SENSORS AND ACTUATORS B-CHEMICAL
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2025
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IF 7.7
Qing Kang,Tong Lin,Jingbo Jiao,Yidi Liu,Yurong Guo,Chenjing Ma,Xinjun Du,Shuo Wang
Salmonella typhimurium ( S. typhimurium ) contamination has become the main source of foodborne diseases and has substantial effects on human well-being. Herein, we present a nucleic acid-responsive colorimetric biosensor for ultrasensitive detection of S. typhimurium , integrating a multifunctional Fe 3 O 4 @Zr-MOF/GOx nanoprobe with exponential amplification reaction (EXPAR). The system integrates glucose oxidase (GOx) encapsulated within a Zr-based metal-organic framework (Zr-MOF) modified with magnetic Fe 3 O 4 nanoparticles. In the presence of S. typhimurium , the EXPAR reaction is triggered, and the controlled release of GOx is achieved by DNA strand displacement. The detection mechanism leverages GOx-catalyzed glucose oxidation to generate H 2 O 2 , which oxidizes 3,3’,5,5’-tetramethylbenzidine (TMB) for colorimetric signal readout. The biosensor demonstrates high specificity for S. typhimurium , with a detection limit of 2.26 CFU mL⁻¹ , and practical applicability in spiked milk samples, achieving recoveries of 89.6–111.5 %. The strategy employing stimuli-responsive DNA/MOF composites demonstrated significant potential in food quality monitoring and analysis.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yujia Zhao,Xianquan Li,Jifeng Pang,Wenguang Yu,Peifang Yan,Yang Su,Lin Li,Mingyuan Zheng
Catalytic conversion of bio-ethanol (EtOH) into 1,3-butadiene (1,3-BD, ETB) represents a low-carbon technology contributing to the sustainable production of renewable 1,3-BD. However, the low selectivity towards 1,3-BD and poor stability of catalysts hinder practical applications of the ETB process. In this work, we presented a novel Zn-Zr catalyst supported on dendrite-structured mesoporous silica (DSMS). Compared to the typical meso- or micro- porous materials such as SBA-15, meso-SiO 2 and Silicate-1 supported catalysts, the Zn-Zr/DSMS catalysts exhibited outstanding catalytic performance and exceptionally high stability in the ETB reaction. Over the representative 0.5%Zn2%Zr/DSMS catalyst, selectivity of 1,3-BD > 65 % and EtOH conversions of 72 %–100 % were obtained at temperatures in a wide range of 350–400 °C. More attractively, the distinguished performance was stable in a long time on stream of 172 h, and able to be effectively restored by calcining the spent catalyst. Systematic characterizations revealed that Zn and Zr species were highly dispersed on the DSMS support nearly at an atomic level, forming abundant Lewis acid sites without Bronsted acidity. This may account for the exceptionally high activity and 1,3-BD selectivity over the 0.5%Zn2%Zr/DSMS catalyst. The unique dendritic structure of the catalyst played important roles in stabilizing the catalytic performance. Correlated to the results of in-situ spectroscopy and conditional experiments, the roles of active sites and the contribution of the catalyst structure were proposed for the ETB process over the Zn-Zr/DSMS catalysts.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Xiaobo Bai,Chengyan Liu,Fucong Li,Zhongwei Zhang,Ying Peng,Ruifan Si,Baoquan Feng,Guojing Wu,Jie Gao,Haiqiao Wei,Lei Miao
Lead-free GeTe-based thermoelectric (TE) materials are most promising candidates to replace the environmentally harmful PbTe for TE application at middle temperature range, where high power factor ( PF ) is significantly important for high power generation if the cost of heat source is low enough. In this study, we report for the first time that the PF of GeTe can be greatly enhanced by tailoring the interaction between Te 5s 2 lone pair and antibonding orbitals, which is induced by the hybridization of Zr 4d 2 electrons with antibonding orbitals. As a result, the contribution of Ge 4s 2 electrons to the valence band is promoted, leading to the band sharpening at the valence band maximum in rhombohedral phase, and simultaneous band sharpening at the valence band maximum and band flattening at the conduction band minimum in cubic phase. Lower band effective mass m b * effectively increases the carrier mobility to a very high value of ∼121 cm −2 V −1 s −1 (300 K), and the Seebeck coefficient is improved by the reduced detrimental effect of minority carrier in cubic phase, enhancing the maximum PF up to a record value of ∼5503 μW m −1 K −1 . With the assistance of reduced thermal conductivity, a peak zT of ∼1.9 is achieved at 673 K, which is one of the highest values among single doped GeTe. This work provides a new guidance to enhance the TE performance of GeTe-based materials.
研究领域:
材料科学
·
物理学
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CHEMICAL ENGINEERING JOURNAL
·
2019
·
IF 8.355
Zhen Huang,Minghu Zhao,Chen Wang,Shixing Wang,Linqing Dai,Libo Zhang,Lei Xu
A novel metal organic framework absorbent was synthesized by one step method using 2,2′-dithiodibenzoic acid as organic linker for efficient and selective recovery of Au(III) from aqueous solution. The adsorbent were detected by scanning electron microscope, X-ray diffraction and zeta potential instruments. Its performance was tested by batch experiments. The adsorption isotherm conforms to the Langmuir model, demonstrating that the adsorption process is the uniform monolayer adsorption. The kinetic model is well fitted to the pseudo second-order dynamics model. The maximum adsorption capacity was 1119 mg/g at pH = 2. High temperatures can promote the absorption process. The five adsorption and desorption cycles indicate that the adsorbent has good repeatability for Au(III) adsorption. It could selectively adsorbed Au(III) from wastewater. The adsorption derive from chelation and reduction. The DFT and XPS results show that Au(III) is mainly adsorbed on the adsorbent by coupling with the S atom. These results indicate that it has a high potential to remove Au(III) from industrial wastewater.
研究领域:
环境科学
·
材料科学
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