MOLECULES
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2022
·Vol. 27
·期 3
·904
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IF 4.927
Gai Zhang,Yufan Zhang,Amin Tan,Yan Yang,Min Tian
Oxidative desulfurization (ODS) is the promising new method for super deep desulfurization of fuel oil. The oxidative desulfurization performance of the metal-N4-chelates metallophthalocyanines (MPcs) is related to the chemical properties of conjugate structures and the central metal ions. Herein, a biomimetic catalytic system composed of metallophthalocyanines (MPcR4, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); R = -H, -COOH, -NO2, -NH2) and molecular O2was performed to study the influence of MN4-type coordination structure in metallophthalocyanines for the degradation of dibenzothiophene (DBT) in model oil containing n-octane. The results reveal that the conjugate structures and the center metal ions of metallophthalocyanines played key roles in oxidative desulfurization performance. The inductive effect of different R substituents strongly affected the electron cloud distribution of the conjugate structures and the catalytic performance. Moreover, the catalytic activity of MPcs, which is related to the d electronic configuration and ligand-field effects, does not sequentially increase with the increase in the d electron number of central metal ions.Keywords:metallophthalocyanine;MN4-type coordination structure;desulfurization;O2
研究领域:
化学
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环境科学
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产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Zhenpeng Liu,Zhe Chen,Jun Bu,Wenxiu Ma,Lei Zhang,Hong Zhong,Lin Cheng,Shuangming Li,Tao Wang,Jian Zhang
Compared to their booming thermocatalytic counterparts, electrocatalytic acetylene semihydrogenation still remain stagnant owing to its low activity and poor selectivity. Here, we first explore metal phthalocyanines (M(Pc)s) featuring a defined metal coordination environment as electrocatalysts for acetylene semihydrogenation. Consequently, CoPc exhibits an ethylene current density of 150.8 mA cm −2 and a ∼ 96% ethylene faradaic efficiency under a pure acetylene stream. In-situ electrochemical Raman and theoretical calculations demonstrate that CoPc favors acetylene absorption/hydrogenation processes. Even for crude ethylene containing 1 × 10 4 ppm acetylene, CoPc manifests a ∼ 99.5% acetylene conversion, a high turnover frequency of 4.86 × 10 –3 s −1 and a large space velocity of 2.4 × 10 5 ml·g cat –1 ·h −1 , outperforming those for reported thermocatalysts. This work facilitates the development of electrocatalytic acetylene semihydrogenation and promises alternatives to traditional thermocatalytic processes.
研究领域:
化学
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材料科学
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电化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2021
·
IF 19.503
Qianglong Qi,Jue Hu,Sitian Guo,Hongchuan Song,Shixing Wang,Yaochun Yao,Thiquynhxuan Le,Wei Li,Chengxu Zhang,Libo Zhang
Although large-scale synthesis of inexpensive and efficient electrocatalysts for oxygen evolution reaction (OER) is critical for industrial water splitting, little attention has been paid to that. Here, FeCo-bimetallic polyphthalocyanine (FeCo-PPc) with ultra-low-cost of less than $0.1 per gram and excellent OER electrocatalytic performance has been prepared in kilogram-scale for the first time. The FeCo-PPc catalyst, around 1/5000th times lower the cost of the commercial IrO 2 , exhibits 24 times higher turnover frequency (0.417 s −1 at 300 mV) and much lower the overpotential (308 mV at 500 mA cm −2 ) than that of IrO 2 (0.0177 s −1 and 588 mV, respectively). Moreover, the FeCo-PPc catalyst shows outstanding long-term stability under an industrial condition (6 M KOH and 85℃) at the high current densities of 100 mA cm −2 and 500 mA cm −2 . The excellent OER activity can be attributed to the electron interaction between Fe and Co and the electronegativity of N atoms, which regulate the electron cloud density of neighboring atoms and form active sites to promote the adsorption of reactants. Our work may guide rational design and large-scale synthesis of electrocatalysts that work well at high current densities in industrial conditions.
研究领域:
材料科学
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电化学
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DOI
高影响因子
Nanomaterials and Nanotechnology
·
2022
·
IF 3.28
Gai Zhang,Yufan Zhang,Amin Tan,Hongwei Zhou,Weifeng Zhao,Weixing Chen
Dinuclear metallophthalocyanines Fe2Pc2(CP)4 containing carboxyl substitutes were wrapped with amino-functionalized carbon nanotubes (MWCNTs-NH2) to enhance electrocatalytic activity for oxygen reduction reaction (ORR) using a facile “in situ” amidation reaction. The morphological characteristics and chemical environment of the Fe2Pc2(CP)4/MWCNTs-NH2 composites were characterized by scanning electron microscope (SEM), X-ray diffraction, Ultraviolet–visible (UV-Vis), Fourier Transform infrared (FTIR), and X-ray photoelectron spectroscopy. The electrocatalytic activity of ORR was tested and analyzed by cyclic voltammetry and linear sweep voltammetry. The results showed that the π–π interactions between the Fe2Pc2(CP)4 and MWCNTs-NH2 dramatically enhanced the π electron density in the conjugated structure, and oxygen could be reduced much more easily. Moreover, the oxygen reduction reactions mainly proceeded a one-step four electron process for Fe2Pc2(CP)4/MWCNTs-NH2 catalysts. The dispersion and electrocatalytic performance of M2Pc2Rn had be enhanced after being loaded on functionalized carbon nanotubes.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
ACS Nano
·
2025
·
IF 16
Shiyuan Xu,Yi Huang,Dannv Ma,Jiaying Wu,Xuemei Liu,Qianru Zhang,Zhuangyue Gu,Aiwu Pan,Jianmin Wu
As a prevalent clinical condition, it is critical to distinguish between bacterial and viral respiratory tract infections given their pivotal role in guiding appropriate pharmaceutical interventions and preventing antibiotic misuse. Exhaled breath (EB) contains a spectrum of disease-specific biomarkers, enabling precise diagnostic analysis. Thus, EB analysis using an electronic nose (e-nose) to record electrical response fingerprints and discriminate pathogens via machine learning algorithms has emerged as a promising noninvasive diagnostic technology. In this study, a graphene-based e-nose sensor array modified with metal−organic frameworks (MOFs) and metal phthalocyanines (MPcs) was developed by using multiple reduction methods. The sensor array demonstrated excellent capability in distinguishing between two types of EB samples collected from healthy individuals spiked with acetone and isoprene, which are closely associated with bacterial and viral respiratory infections. Furthermore, a diagnostic model was constructed using e-nose fingerprints from 145 clinical EB samples comprising 89 bacterial infection cases and 56 viral infection cases. A weighted fusion classification model, integrating the support vector machine, random forest, and Lasso regression (Lasso), achieved an accuracy of 83.7% in the validation group, with an area under the curve (AUC) of 0.87. An independent external clinical trial involving 43 respiratory infection patients (including 6 unidentified cases) yielded an accuracy of 75.7% and an AUC of 0.81 for distinguishing bacterial from viral infections. Additionally, the sensor array achieved a 75% accuracy rate in discriminating mycoplasma infections by using linear discriminant analysis. These results suggest that the graphene-based e-nose array modified with MOFs and MPcs is a promising tool for diagnosing respiratory tract infections, aiding in optimized treatment decisions and potentially improving therapeutic efficiency.
研究领域:
医学诊断
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材料科学
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机器学习
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产品关联
DOI
PubMed
高影响因子
FUEL
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2018
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IF 4.908
Juan Zhang,Shuang Sun,Yuhang Bian,Weikang Li,Ran Liu,Dishun Zhao
Four metal phthalocyanines (Pc-4, 8, 12, 16) functionalized ionic liquids were polymerized on the surface of silica gel as adsorbent materials. They were characterized by FT-IR, BET, SEM and TEM measurements. The characterization results proved that the adsorbents were prepared successfully. Their adsorptive desulfurization performances to dibenzothiophene in model oil at room temperature and atmospheric pressure were investigated in detail. The results showed that the adsorptive desulfurization effect of P-4 was best. The optimal amount of adsorbent was 10 g/100 mL model oil. The maximum amount of DBT adsorbed was 52.41 mg/g, superior to some previously reported adsorbents. The adsorption equilibrium and kinetics of this adsorbent were also examined. The adsorption behavior fitted well to Freundlich isotherm model, pseudo-second-order kinetics model and Weber and Morris kinetics model. Adsorption and regeneration by solvent processes were performed 10 times, and the adsorption capacity of the adsorbent did not decrease obviously. P-4 also had a good adsorption effect on different sulfur compounds, and the order of removal was DBT > BT > 2-MTH > TH.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
Science China-Materials
·
2021
·Vol. 65
·期 1
·155-162
·
IF 8.273
Yang Chenhuai,Gao Zengqiang,Wang Dingjia,Li Shuyu,Li Junjun,Zhu Yating,Wang Haiqing,Yang Wenjuan,Gao Xuejiao J.,Zhang Zhicheng,Hu Wenping
Heterogeneous molecular catalysts, such as metal phthalocyanines, are efficient electrocatalysts for CO 2 reduction reaction (CO 2 RR). However, the rational design and synthesis of a molecular catalyst-based heterostructure for CO 2 RR remains challenging. Herein, we developed a crystalline bimetallic phthalocyanine heterostructure electrocatalyst (CoPc/FePc HS), which achieved an excellent CO 2 -to-CO conversion efficiency (99%) and outstanding long-term stability after 10 h of electrocatalysis. Density functional theory calculations revealed that the enhancement of CO 2 RR performance could be attributed to the distinct electron transfer pattern between FePc and CoPc. The heterostructural engineering in molecular catalysts would inspire a unique approach for improving CO 2 RR performance.
研究领域:
材料科学
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电化学
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催化科学
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产品关联
DOI
高影响因子
CELLULOSE
·
2021
·Vol. 29
·期 2
·849-861
·
IF 5.044
Chen Shiliang,Wu Zhijing,Fan Qiujin,Huang Jiachi
Abstract The understanding of interaction between graphene oxide (GO) and bacterial cellulose (BC) at molecular level is indispensable for meeting the goal of constructing a graphene-oxide-bacterial-cellulose (GOBC) nanohybrid and the fabrication of GOBC-based functional nanocomposites. In this paper, a GOBC with hierarchical three-dimensional (3D) framework was designed as a substrate for the metal phthalocyanine (Pc) catalyst. This substrate caused a remarkable enhancement of the catalysis of organic dye molecules. Firstly, GOBC was conveniently fabricated with one-step biosynthesis. The interaction mechanism at the molecular level between GO and BC was modeled with DFT quantum mechanics calculations that followed semi-empirical molecular dynamics studies to propose a structure. The formation of hydrogen-bond between O(3)-H and O(6)-H of BC and oxygen atom of GO was verified by core valence bifurcation and revealing noncovalent interactions theoretical analysis. Graphene-bacterial-cellulose (GBC) nanohybrid was then prepared by brief reduction of GOBC with N 2 H 4 and used for the direct immobilization of Pc catalyst. The catalytic activity of the Pc that was immobilized on the GBC nanohybrid was evaluated based on its catalytic oxidation of organic dyes, and a remarkable enhancement of the catalytic activity by the GBC substrate was observed. The electron transfer and the electrical structure state of the catalytic system were investigated by charge density difference and density of states theoretical calculations. An innovative catalytic mechanism of “substrate-driven enhancement” of the highly reactive metal phthalocyanine immobilized graphene-bacterial-cellulose nanocomposite was proposed based on both experimental and theoretical calculation results.
Graphical abstract
研究领域:
材料科学
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化学工程
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生物技术
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DOI
高影响因子
RSC Advances
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2022
·Vol. 12
·期 10
·5964-5970
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IF 4.036
Hongyu Cao,Meina Gong,Mengyan Wang,Qian Tang,Lihao Wang,Xuefang Zheng
The large conjugated system and the d orbitals of metallic phthalocyanines (MPcs) are easily triggered by solvent molecules and light to cause variations in photo-physical and photo-chemical properties. To clarify the novel properties of photo-excited MPcs in solvents, the steady/transient state spectral data were collected to investigate four MPc templates, including FePc, ZnPc, CoPc and AlClPc. The Q bands of FePc and CoPc were prone to redshift, while the peaks of ZnPc and AlClPc tended to blueshift in various solvents compared with that in DMSO. With xenon lamp irradiation, the characteristic absorption peak intensity of FePc and ZnPc in DMSO decreased gradually and then increased after being subjected to dark condition. The transient absorption spectra and kinetic data illustrated that photo-excited FePc and CoPc produced relatively short lifetime transient intermediates. The positive absorption at 650 nm in the Q bands of FePc and CoPc could be assigned to the d–π* electron transition in transient intermediates with unpaired d-orbital electron in the open shell configuration of Fe2+ and Co2+. The above studies were of great significance for the application of solvent-triggered and photo-induced novel properties of MPcs.
研究领域:
化学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MOLECULES
·
2024
·Vol. 29
·期 2
·347
·
IF 4.2
Fangli Du,Xuequan Xian,Peiduo Tang,Yanming Li
A sulfonyl-chloride-modified lignin-based porous carbon-supported metal phthalocyanine catalyst was prepared and used to replace the traditional Fenton’s reagent for lignin degradation. The catalyst underwent a detailed characterization analysis in terms of functional group distributions, surface area, morphological structure, via FT-IR, XPS, BET, and SEM. The catalyst possessed a specific surface area of 638.98 m2/g and a pore volume of 0.291 cm3/g. The prepared catalyst was studied for its ability of oxidative degradation of lignin under different reaction conditions. By optimizing the reaction conditions, a maximum liquid product yield of 38.94% was obtained at 135 °C with 3.5 wt% of catalyst and 15 × 10−2mol/L H2O2; at the same time, a maximum phenols selectivity of 32.58% was achieved. The compositions and properties of liquid products obtained from lignin degradation using different catalyst concentrations were studied comparatively via GC-MS, FT-IR,1H-NMR, and EA. Furthermore, the structure changes of solid residues are also discussed.
研究领域:
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
VIBRATIONAL SPECTROSCOPY
·
2018
·
IF 1.363
Xiaofang Zhang,Weihua Lin,Haofei Zhao,Rongming Wang
Metallophthalocyanine (MPc) derivatives show excellent photoelectric and magnetic properties due to their large π-conjugate system. Central metals and peripheral substituents are two important ways to adjust and optimize the properties of MPc via tuning the large π-conjugate system. In this work, Raman scattering spectra of MPc, including ZnPc, CuPc, CoPc, and NiPc, were investigated. The most intense band in the Raman spectra at about 1500 cm −1 , owing to the vibration of C N C bridge bonds, shifts significantly with the size of the metal ion , indicating a good marker of metal ion effect on the changes of the Raman shift. For the MPc with suitable sizes of metal ions (e.g., Zn 2+ , Cu 2+ , Co 2+ , Ni 2+ ), the structure of phthalocyanine ring is planar. The ring will be distorted according to the different forces of the central metal ions. When the polarization force of the central metal ion enhances (Zn 2+ < Cu 2+ < Co 2+ < Ni 2+ ), the Raman shift of C N C would simultaneously increase, and the bigger polarization force could lead to a larger Raman shift (ZnPc < CuPc < CoPc < NiPc). On the other hand, the C N C Raman shift of the 3-substituted MPc was relatively smaller than that of the 4-substituted one with the same central metal ion. When the electron density of the phthalocyanine ring was relatively low, the energy of the system would increase and the Raman peak would correspondingly shift distinctly. Our Raman spectra results are consistent with the UV–vis measurement results. This work will provide the basis for structure analysis, and design of new molecular materials, as well as their application.
研究领域:
材料科学
·
光谱学
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DOI
高影响因子
RSC Advances
·
2016
·Vol. 6
·期 79
·75632-75639
·
IF 3.289
Weixing Yang,Ronglan Zhang,Kai Luo,Weiping Zhang,Jianshe Zhao
A series of metal 2,9,16,23-tetraaminophthalocyanines [TAPcM, M = Cu(II), Ni(II), Zn(II), Fe(II), Mn(II)] have been prepared and used to chemically modify fluorinated multi-walled carbon nanotubes (F-MWCNTs). The generated composites TAPcM/MWCNTs were characterized by IR, UV-Vis and XRD. The electrocatalytic activity of all the composites was evaluated by adding them into the electrolyte of the Li/SOCl2 battery and taking cyclic voltammograms in simulated circumstances. The results show that the composites can dramatically improve the capacity of the battery, and their electrocatalytic performance strongly depends on the metal phthalocyanine species. The order of the electrocatalytic activity of 2,9,16,23-TAPcM and 2,9,16,23-TAPcM/MWCNTs with different metal ions in the center is Mn(II) > Ni(II) > Zn(II) > Fe(II) > Cu(II). The excellent electrocatalytic performance of the modified F-MWCNTs may be due to the fine synergistic effect between the metal phthalocyanines and the MWCNTs.
研究领域:
材料科学
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电化学
✓ 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）