JOURNAL OF MOLECULAR STRUCTURE
·
2026
·
IF 4.9
Qiao Li,Dong-Xu Cui,Yanli Leng,Shou-Jun Lai,Tingting Deng,Teng Niu,Shixia Yang,Hongru Dong
A naphthalene-benzothiazole probe (Q) for dual-channel sulfite detection was developed. • DFT calculations confirmed a kinetically dominant Michael addition at the C11 site. • Activation energy for the C11 pathway (16.11kcal/mol) is lower than alternative sites. • Hole-electron analysis revealed an ICT-to-LE transition during fluorescence quenching. The design and synthesis of a D–π–A type fluorescent probe based on a naphthalene-benzothiazole scaffold, for the colorimetric and fluorometric detection of sulfite (SO₃²⁻), are reported. Probe Q exhibits a selective response toward sulfite in DMSO H₂O (7:3, v/v) solution, with a detection limit of 0.42 μM. The reaction mechanism, evaluated through DFT and TD-DFT calculations using a benchmarked PBE0 functional, identifies several potential nucleophilic attack sites (C11, C14, and C16). Transition state and intrinsic reaction coordinate analyses confirm that the Michael addition at the C11 site is the kinetically dominant pathway, with an activation energy of 16.11 kcal/mol. Furthermore, combined hole-electron and excited-state analyses, based on vertical excitation calculations and oscillator strengths, reveal that the fluorescence quenching originates from a transition of the S₁ state from a bright intramolecular charge transfer (ICT) state to a non-radiative state upon sulfite addition. This study provides a molecular-level, synergistic experimental and theoretical framework for the rational design of reaction-based fluorescent probes.
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高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2024
·
IF 3.5
Hu Quanli,Su Wang,Luo Hanqiong,Wang Yin,Liu Jinghai
The electrospun light rare earth orthochromites RCrO 3 (R = La, Pr, Nd, Sm, Eu) nanofibers have perovskite-type orthorhombic structures. Raman spectra proved the typical vibration modes of the rotation, bending, and stretching of the CrO 6 octahedra in RCrO 3 nanofibers. The rare earth element with large ion radius, low electronegativity, and remarkable affinity for oxygen, and the rich redox reaction of Cr endow RCrO 3 a potential energy storage material for supercapacitors. It is highly significant to investigate the electrochemical properties of RCrO 3 . The electrochemical properties of the RCrO 3 nanofibers as supercapacitor electrodes were elucidated. At 0.5 A/g, the LaCrO 3 , PrCrO 3 , NdCrO 3 , SmCrO 3 , and EuCrO 3 nanofibers exhibited the specific capacitance values of 267.8, 132.8, 157.6, 170.5, and 170.4 F/g, respectively. First-principles density functional theory method was used to clarify the electronic structure and total density of states of the RCrO 3 nanofibers. This study provides a rational design and fabrication method to pseudocapacitor electrodes.
研究领域:
材料科学
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电化学
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理论计算
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高影响因子
MOLECULAR PHYSICS
·
2022
·
IF 1.937
Haowen Zhang,Liyun Ding,Yumei Zhang,Tian Wu,Qin Li
Cellulose acetate(CA)/graphene oxide (GO) composites have been widely used in the drug development and biosensing due to its excellent biocompatibility and strength. It is important to study their adsorption mechanisms for the application of CA/GO in detail. Here, the interaction between GO and CA was described by DFT simulations, and CA/GO composite films were characterised using tensile testing and FTIR spectroscopy. DFT calculations indicated that there is no chemical bonding between CA and GO adsorption but hydrogen bonding from hydroxyl groups facilitates the adsorption process. FTIR of CA/GO results show that the characteristic peaks of hydroxyl groups in the composite film is shifted towards high frequencies compared to the pure CA film, which is a strong evidence of hydrogen bonding of hydroxyl groups during the adsorption process. The tensile test results indicate that hydrogen bonds contribute to the tensile strength and elastic modulus of the CA/GO composite film.
研究领域:
材料科学
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生物医学工程
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Xingyuan Wan,Kaixi Jiang,Ting'an Zhang,Kun Wang,Han Yang,Shengnan Lin
Upgrading copper slag into value-added products provides an untapped opportunity to address arsenic pollution in the environment and promote waste recycling, but the problem of excessive arsenic in products remains a huge engineering challenge. Herein, we employ DFT calculations to explore the dissociation mechanism of AsMA and propose a universal descriptor for screening As removal agents for the first time. The dissociation of AsMA is related to the disturbance of the Mo-As bond by Ba and follows the “Perturbation – Re-stabilization – Dissociation” mechanism. The B Ψ value of Ba is near the minimum value of −0.1058 in the universal descriptors, which renders it potential candidates for As removal agents. As expected, Ba can increase As removal efficiency by approximately 45 % when employing the Si-Ca-Ba alloy compared to other Ca-based alloys. This work offers contributions to the As removal technology for copper slag value-added products while also highlighting the DFT calculations used in guiding engineering practices.
研究领域:
环境科学
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材料科学
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化学工程
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DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2024
·
IF 10.8
Wanli Lian,Guanghui Yu,Jie Ma,Juan Xiong,Cuiyun Niu,Ran Zhang,Haijiao Xie,Liping Weng
Despite extensive study, geochemical modeling often fails to accurately predict lead (Pb) immobilization in environmental samples. This study employs the Charge Distribution MUlti-SIte Complexation (CD-MUSIC) model, X-ray absorption fine structure (XAFS), and density functional theory (DFT) to investigate mechanisms of phosphate (PO4) induced Pb immobilization on metal (hydr)oxides. The results reveal that PO4 mainly enhances bidentate-adsorbed Pb on goethite via electrostatic synergy at low PO4 concentrations. At relatively low pH (below 5.5) and elevated PO4 concentrations, the formation of the monodentate-O-sharing Pb-PO4 ternary structure on goethite becomes important. Precipitation of hydropyromorphite (Pb5(PO4)3OH) occurs at high pH and high concentrations of Pb and PO4, with an optimized log Ksp value of −82.02. The adjustment of log Ksp compared to that in the bulk solution allows for quantification of the overall Pb-PO4 precipitation enhanced by goethite. The CD-MUSIC model parameters for both the bidentate Pb complex and the monodentate-O-sharing Pb-PO4 ternary complex were optimized. The modeling results and parameters are further validated and specified with XAFS analysis and DFT calculations. This study provides quantitative molecular-level insights into the contributions of electrostatic enhancement, ternary complexation, and precipitation to phosphate-induced Pb immobilization on oxides, which will be helpful in resolving controversies regarding Pb distribution in environmental samples.
研究领域:
环境科学
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地球化学
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DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
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2024
·
IF 5.3
Lianjing Mao,Xiaolong Zhou,Tianyu Zheng,Xiao Li,Xiufang Wang,Zhiyu Zhao,Wei Sun,Pengrui Zhang,Jinhe Sun
The metal ion extraction process is usually accompanied by the removal of coordinated water molecules and the change of water content in the extraction phase. However, hierarchical methodologies on water research are incredibly sparse, restricting a thorough knowledge of the extraction mechanism. It was clarified the diversity of water occurrence forms in the extraction phase and quantitative relationship between water, Li + and crown ether based on the (B12C4/B15C5/B18C6-[EMIm][NTf 2 ])-LiNTf 2 solvent extraction system. While the complexation mechanism between hydrated Li + and crown ether was discussed carefully. Firstly, it demonstrated that the water content of the extraction phase: B18C6 > B15C5 > B12C4. Secondly, the water in the extraction phase is mainly collected by solvent and crown ether, with the latter catching water primarily via Li + coordination and weak interactions. In the end, focusing on the water captured by the crown ether through Li + coordination, slope analysis and DFT calculations found that Li (H 2 O) 4 + was removed three water molecules to complex with B12C4 or B15C5, whereas B18C6 tends to remove two water molecules. It is precious for a thorough grasp of the mechanism and procedure of Li + extraction by crown ethers. What’s more, it offers novel strategies for investigating water content and transfer mechanisms in extraction systems.
研究领域:
化学
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材料科学
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理论研究
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DOI
高影响因子
Journal of Energetic Materials
·
2024
·
IF 1.7
Ying Wu,Yong Liu,Shuai Hou,Qizhi Zhao,Han Gao,Xiao Yan
4,4’-Azo-1,2,4-triazole (atrz) is a new high nitrogen energetic material with high energy density, high gas yield and wide application prospects, but the low synthesis temperature and long time are the main reasons limiting its application. To achieve efficient synthesis of atrz, the double drop synthesis method was designed to solve the problem of unstable concentration of oxidant (HClO) due to batch feeding. The reaction temperature, reaction time, and molar ratio of reactants of n(4-amino-1,2,4-triazole):n(ClO−) were studied and optimized using the single factor variable method; Characterization and analysis of atrz using theoretical calculations with elemental analysis, infrared spectroscopy, crystal morphology, and nuclear magnetic resonance; The thermal properties and stability of atrz were tested and analyzed using TG-DTA. The results showed that the reaction time of the double drop synthesis method was shortened from 5 hours to 1.5 hours under the conditions of similar yield, and the efficiency was increased by 2.3 times. The optimized process was a reaction temperature of 5°C-10°C, reaction time of 1.5 hours, n(4-amino-1,2,4-triazole):n(ClO−) of 1:2, and the yield reached 73%. The product was white, needle-like crystals, which were determined to be atrz by means of characterization and theoretical calculations. Atrz’s decomposition peak temperature is 309.0°C, and when the temperature is below 271.7°C, atrz is thermally stable. The activation energies of atrz calculated by Kissinger and Flynn-Wall-Ozawa methods were 195.0 kJ·mol−1 and 194.6 kJ·mol−1.
研究领域:
化学
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材料科学
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能材料
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理论计算
·
热分析
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DOI
高影响因子
MOLECULES
·
2024
·Vol. 29
·期 7
·1490
·
IF 4.2
Qiang Song,Xiong Tong,Pulin Dai,Xian Xie,Ruiqi Xie,Peiqiang Fan,Yuanlin Ma,Hang Chen
In industrial manufacturing, pyrrhotite(Fe1−xS), once depressed, is commonly activated for flotation. However, the replacement of CuSO4is necessary due to the need for exact control over the dosage during the activation of pyrrhotite, which can pose challenges in industrial settings. This research introduces the use of FeSO4for the first time to efficiently activate pyrrhotite. The impact of two different activators on pyrrhotite was examined through microflotation experiments and density functional theory (DFT) calculations. Microflotation experiments confirmed that as the CuSO4dosage increased from 0 to 8 × 10−4mol/L, the recovery of pyrrhotite initially increased slightly from 71.27% to 87.65% but then sharply decreased to 16.47%. Conversely, when the FeSO4dosage was increased from 0 to 8 × 10−4mol/L, pyrrhotite’s recovery rose from 71.27% to 82.37%. These results indicate a higher sensitivity of CuSO4to dosage variations, suggesting that minor alterations in dosage can significantly impact its efficacy under certain experimental conditions. In contrast, FeSO4might demonstrate reduced sensitivity to changes in dosage, leading to more consistent performance. Fe ions can chemically adsorb onto the surface of pyrrhotite (001), creating a stable chemical bond, thereby markedly activating pyrrhotite. The addition of butyl xanthate (BX), coupled with the action of Fe2+on activated pyrrhotite, results in the formation of four Fe-S bonds on Fe2+. The proximity of their atomic distances contributes to the development of a stable double-chelate structure. The S 3p orbital on BX hybridizes with the Fe 3d orbital on pyrrhotite, but the hybrid effect of Fe2+activation is stronger than that of nonactivation. In addition, the Fe-S bond formed by the addition of activated Fe2+has a higher Mulliken population, more charge overlap, and stronger covalent bonds. Therefore, Fe2+is an excellent, efficient, and stable pyrrhotite activator.
研究领域:
矿物加工工程
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理论化学
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DOI
PubMed
高影响因子
CERAMICS INTERNATIONAL
·
2025
·
IF 5.6
Xu Zhang,Shuting Li,Jiyang Zhang,Jihong Liu,Chaoyang Huang,Jiapeng Zhu,Guixiao Jia,Shengli An
CeO 2 is a promising electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Studies have found that F-doping improves its ionic conductivity, but the underlying mechanisms remain unclear. Therefore, this study employs a DFT+U method to calculate geometrical and electronic structures and oxygen ion migrations of Gd-, Ca- and F-dopings co-doped CeO 2 . The calculated results are verified by our experiment. DFT calculations find that oxygen vacancies (V) are easily formed at next-neighboring sites near the F - ions, different with the case of Gd- and Ca-doped CeO 2 . Gd-, Ca- and F-dopings strengthen Ce-O bonds, inconstant with the result from the reported experimental hypothesis for the F-doping. The F-doping restrains the change of Ce 4+ to Ce 3+ . Migration energy barriers E m of oxygen ions are mainly affected by the migration distances and peripherally done by the oxygen vacancy cavity size and the defect association. Due to the lager oxygen vacancy cavity size and the smaller defect association in CGOF and CGOCF, the F-dopings have the smaller E m . This is contrary to the speculation of the reported experimental study based on the electronegative comparison of F and O. Our experiment finds that Ca and F co-doping significantly increases the conductivity, 3.9 times of the conductivity of Gd-doped CeO 2 . The study clarifies the nature mechanism of the ionic conductivity in doped CeO 2 , offering atomic-level insights to aid the development of high-performance CeO 2 -based electrolytes.
研究领域:
材料科学
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能源科学
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高影响因子
Scientific Reports
·
2022
·Vol. 12
·期 1
·1-8
·
IF 4.996
Wu Junsheng,Zhao Zhuo,Zhou Yanwen
Tin-based perovskite material is the best choice to replace heavy metal element lead during the last several years. Cs 2 SnI 6 with Sn 4+ is a fascinating optoelectronic material, which is a more air-stable composite cesium tin halide peroxide variant from CsSnI 3 . However, the optoelectronic performance between N and P type of Cs 2 SnI 6 varies considerably. Herein, we synthesized uniform Cs 2 SnI 6 by modified two-step method, which thermal evaporated CsI firstly, and followed annealing in the SnI 4 and I 2 vapor at 150 °C resulted in uniform Cs 2 SnI 6 films. SnF 4 is used as a dopant source to improve the optoelectronic properties of Cs 2 SnI 6 films. Results indicate that good crystallinity was obtained for all films and the doped films underwent a crystalline plane meritocracy transition. The doped films had a flat, non-porous morphology with large grains. The high transmittance of the doped films in the infrared region led to the avoidance of self-generated thermal decomposition. With the help of F − , the films became more conductive and had higher carrier mobility. DFT calculations showed that doping with F reduced the surface energy of (004), resulted in a preferred orientation transition in the crystal of Cs 2 SnI 6 . Fluorine doped double layer perovskite materials would have a broader application prospect.
研究领域:
材料科学
·
物理化学
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DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Tuo Zheng,Haiyan Fan,Jia Zhao,Jile Fu,Songshou Ye,Sajid Ali,Nuowei Zhang,Jinbao Zheng,Binghui Chen
In diesel adsorption desulfurization, the coordination bonding between the adsorbent and sulfur compounds is interfered by aromatic compounds in diesel. Transition metal cation exchanged zeolites Y has exhibits exceptional anti-interference performance. In this work, the influence of electron configuration on coordination bonding is explored, specifically between the adsorbent and substrate, using both experimental and DFT theoretical methods. Initially, NiY, CuY and ZnY were synthesized and evaluated for their desulfurization performance in model solution (sulfur content: 25 ppmw dibenzothiophene [DBT]) with two toluene concentrations (1 w% and 3 w%). It is found that CuY showed the highest performance with retention rate at 70.2 %. Subsequently, DFT calculations revealed the binding energy between Cu(II) and DBT was −2.71 eV, higher than Ni(II) and Zn(II), and that between Cu(II) and toluene was −1.75 eV, lower than Ni(II) and Zn(II), indicating that the highest binding energy difference was responsible for the best adsorption capability. Apart from these, wave function analysis show the electron configuration between Cu(II) and DBT had the highest binding energy difference. Finally, the impact of electron configuration on adsorption performance is further investigated by modulating the electron configuration of Ni(II) to enhance/suppress its adsorption capability. According to the findings of this study, tuning the electron configuration is an effective strategy to develop materials in adsorptive desulfurization particularly for extra low sulfur content.
研究领域:
化学工程
·
材料科学
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DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 7
·1031
·
IF 3.9
Jie Lin,Yihong Ding,Huile Jin,Tianbiao Zeng
Nickel, cobalt, and manganese oxides are easily obtainable non-noble metal catalysts for water splitting. However, the relationship between composition and catalysts’ performance still needs systematic studies. Herein, guided by theoretical calculations, a low overpotential, easily prepared Mn-doped Co3O4was deposited on graphite plates for water splitting. The 30% Mn-doped Co3O4(Co2.1Mn0.9O4) required the lowest overpotential for oxygen evolution reaction (OER), in which the Co2.1Mn0.9O4reached 20, 30, and 50 mA cm−2in the overpotentials of 425, 451, and 487 mV, respectively, with 90% IR compensation. Under overall water-splitting conditions, the current density reached 30 mA cm−2at an overpotential of 0.78 V without IR compensation. Charge density difference analysis illustrates that doped Mn provides electrons for O atoms, and that Mn doping also promotes the electron fluctuation of Co atoms. XPS analysis reveals that Mn-doping increases the chemical valence of the Co atom, and that the doped Mn atom also exhibits higher chemical valence than the Mn of Mn3O4, which is advantageous to boost the form of based-OOH* radical, then decrease the overpotential. Considering the particular simplicity of growing the Co2.1Mn0.9O4on graphite plates, this work is expected to provide a feasible way to develop the high-performance Co-Mn bimetallic oxide for water splitting.Keywords:water splitting;bimetallic oxides;Mn-doped Co3O4;DFT calculation
研究领域:
材料科学
·
电化学
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高影响因子
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