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    10 April 2022, Volume 43 Issue 4
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.43 No.4(2022)
    2022, 43(4):  1-6. 
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    Inorganic Chemistry
    Synthesis and Luminescence Properties of Cr,In Co-doped Small Size MgGa2O4 Near-infrared Persistent Luminescence Nanoparticles
    SUN Xuefeng, RENAGUL Abdurahman, YANG Tongsheng, YANG Qianting
    2022, 43(4):  20210850.  doi:10.7503/cjcu20210850
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    Cr, In co-doped MgGa2O4 persistent luminescence nanoparticles(PLNPs) with small-size were prepared by ethylene glycol assisted co-precipitation. The influence of Cr,In co-doping and calcination temperature on the MGO crystal structure, afterglow luminescence properties and size were further investigated. The results showed that the optimal Cr,In co-doped concentrations were 0.3% and 0.02%, respectively, and the samples belonged to Fd3m space group, Cr,In co-doping had no effect on the structure of the samples. The PLNPs had a good water dispersibility with an average particle size of (8.61±2.23) nm and the optimum calcination temperature of 700 ℃. Moreover, the afterglow decay life was prolonged by In doping, and the average luminescence life(τav) of the afterglow decay fitting curves increased from 49.33 s to 52.89 s with the QY increased to 44.9%. The activation energy(Ea) was (0.36±0.04) eV. The PLNPs had a good thermal stability, and the trap depth was 0.696 eV. Moreover, the PLNPs had three excitation bands at 260, 410 and 600 nm, respectively, which indicated that UV light, blue-green light and red light could be excited, and the emission wavelength was all at 705 nm, belonged to the 2E2G)→4A24F) transition of Cr3+. Therefore, the PLNPs had a great potential application value in red LED lamps, optical storage devices and biomedical fields.

    Activation of Biochar from Cattail and the VOCs Adsorption Application
    WANG Hongning, HUANG Li, QING Jiang, MA Tengzhou, JIANG Wei, HUANG Weiqiu, CHEN Ruoyu
    2022, 43(4):  20210824.  doi:10.7503/cjcu20210824
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    Biochar was achieved by using cattail as raw material and activated with different agents. The specific surface area and pore volume of biochar before activation was very small, 1.71 m2/g and 0.00421 cm3/g, respectively, and they were greatly increased after activation. The biochar activated by Na2CO3 has the best surface area and pore volume. At the same time, the effects of different mass ratios of Na2CO3 and Biochar on the activation of Biochar were studied, and the optimal mass ratio of activation was determined. When mass ratio of Na2CO3/Biochar is 3∶1, the synthesized dample(Biochar-Na2CO3-3) has the biggest specific surface area and pore volume(624 m2/g and 0.211 cm3/g), which has excellent adsorption performance of volatile organic compounds(VOCs). The static n-hexane, toluene and No.92 gasoline adsorption capacities of Biochar-Na2CO3-3 are 1.03, 0.814 and 0.751 g/g, respectively. The dynamic n-hexane and toluene adsorption capacities of Biochar-Na2CO3-3 are 1.00 and 0.796 g/g, respectively. The adsorption performance is stable, which is better than the commercial activated carbon(AC) and silica gel(SG).

    Analytical Chemistry
    Separation and Characterization of Polymer Blends Using Online Ultra-high Performance Liquid Chromatography-Size Exclusion Chromatography
    WANG Mingfang, FU Hua, FU Zhibo, WANG Yuerong, ZHANG Hongyang, ZHANG Min, HU Ping
    2022, 43(4):  20210865.  doi:10.7503/cjcu20210865
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    The characterization of polymer blends is a difficult problem in adhesives and coatings industry, and the studies on the separation of complex mixtures are always popular. In this paper, an online ultra-high performance liquid chromatography-size exclusion chromatography(UHPLC-SEC) system was designed and set up. The solvent compatibility and orthogonality of the two-dimensional chromatography system were investigated using the hydroxyl polybutadiene(HTPB). The applicability of the two-dimensional chromatography was studied in the separation and characterization of each fraction from the styrene-butadiene block copolymer(SBS), styrene-isoprene block copolymer(SIS) and polymethacrylate(PMMA) blends. The results showed that the molecular weight and distribution of HTPB were determined by UHPLC-SEC, which were consistent with those determined by SEC. The peak molecular weight(Mp), the weight average molecular weight(Mw) and the polymer dispersity index(PDI) of HTPB were 3407 Da, 6573 Da and 2.36, respectively, and the relative standard deviations(RSDs) were less than 5.7%. Moreover, the solvent compatibility and orthogonality of the system were good. Compared to the existing SEC method, the relative errors of MpMw and PDI of PMMA, SBS and SIS fraction measured by UHPLC-SEC were all less than 7.1%. The PMMA remained stable after the mixture of PMMA, SBS and SIS was heated at 200 ℃ for 3 h, while SBS and SIS components degraded significantly. Due to the good accuracy and reproducibility of the UHPLC-SEC method in the characterization of the polymer blends, it is suitable for the failure analysis of the polymer formulations.

    Solution-gated Graphene Field Effect Transistor Sensor Based on Crown Ether Functionalization for the Detection of Mercury Ion
    CAO Lei, CHEN Meijun, YUAN Gang, CHANG Gang, ZHANG Xiuhua, WANG Shengfu, HE Hanping
    2022, 43(4):  20210688.  doi:10.7503/cjcu20210688
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    Hg2+ is a heavy metal with bioaccumulation and toxicity, causing serious damage to the environment and human health. Therefore, it is very necessary to develop a convenient Hg2+ sensor. Because of the excellent performance of graphene field-effect transistors, this work prepared a solution-gated graphene field effect transistor (SGGT) sensor with crown ether functionalized gate. The selectivity of the transistor sensor was achieved through the size effect of crown ether and the chelation of N and S atoms on the crown ether, which makes the sensor recognize Hg2+ specifically. The research showed that the SGGT sensor is more sensitive than traditional electrochemistry due to its inherent signal amplification function, which is 2—3 orders of magnitude lower, and the detection limit is as low as 1×10-12 mol/L in this study. In the detection range of 1×10-12—1×10-7 mol/L, the result exhibited an excellent linear relationship between the change value of the Dirac point and the logarithm of the target concentration. Moreover, it showed extremely high selectivity to Hg2+. The test of the real samples in the lake water was satisfactory, in which the detection standard deviation of Hg2+ is 1.10%—3.77%. The study indicated that the transistor sensor can detect Hg2+ in complex samples with high selectivity and sensitivity.

    Physical Chemistry
    Preparation and Photoelectrochemical Performance of BiVO4/CuBi2O4 Thin Film Photoanodes
    LIU Jiaqi, LI Tianbao
    2022, 43(4):  20220017.  doi:10.7503/cjcu20220017
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    The poor separation and significant recombination of electron-hole pairs and slow transfer mobility of charge carriers limit the performance of BiVO4 for photoelectrochemical(PEC) water splitting. Herein, we present the ternary metal oxide deposition of p-type CuBi2O4 as a route to obtain a novel photocatalyst layer on BiVO4 to form n-BiVO4/p-CuBi2O4 a novel composite photoanode for PEC water splitting. It is found that BiVO4/CuBi2O4 and BiVO4/CuBi2O4/Co-Pi thin films addition show better PEC performance compared with bare BiVO4 under visible illumination. At 1.23 V(vs. RHE) potential, BiVO4/CuBi2O4 thin film show excellent PEC water oxidation performance, and the photocurrent density reaches 2.8 mA/cm2. The photocurrent density of BiVO4/CuBi2O4/Co-Pi thin film loaded with cobalt-phosphate(Co-Pi) reaches 4.45 mA/cm2. The curront densities are 3.1 times and 4.9 times of bare BiVO4, respectively. BiVO4 and CuBi2O4 construct a p-n heterojunction to boost its poor electron-hole separation and transport properties using the built-in electrical potential. The X-ray diffraction(XRD), UV-Vis measurements, electro-chemical impedance spectroscopy(EIS) and schematic diagram of band structure absorption spectra reveal the enhanced PEC performance and light stability of the prepared electrode materials, when it is applied to PEC water splitting. Based on the study, we have gained an in-depth understanding of the BiVO4/CuBi2O4 and BiVO4/CuBi2O4/Co-Pi composite as high potential in efficient PEC water splitting devices.

    Synthesis of Ultrathin Sm-MOF Nanosheets and Their Visible-light Induced Photodegradation of Mustard Simulant
    FENG Li, SHAO Lanxing, LI Sijun, QUAN Wenxuan, ZHUANG Jinliang
    2022, 43(4):  20210867.  doi:10.7503/cjcu20210867
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    Ultrathin metal-organic frameworks(MOFs) nanosheets are excellent heterogeneous catalysts owing to their unique structural properties, such as high density and exposed surface active sites, short diffusion distance for reactants/products. Herein, by the employment of photoactive 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H4TBAPy) as ligand and lanthanide metal ion Sm3+ as metal node, and benzoic acid as modulator, ultrathin two-dmensional Sm-TBAPy nanosheets were synthesized by microwave method. The morphological and structural information of Sm-TBAPy nanosheets were characterized by SEM, TEM, XRD, UV-Vis DRS, FTIR and N2 adsorption-desorption techniques. The as-synthesized Sm-TBAPy are monodispersed nanosheets with size of 200 nm and thickness of 12 nm. The BET specific surface area is 163 m2/g, and the bandgap is 2.62 eV. Sm-TBAPy nanosheets enable selective photocatalytic conversion of 2-chloroethyl ethyl sulfide(CEES) into CEESO under blue light irradiation at room temperature in the presence of oxygen. The catalysts can be reused for 4 times without significantly decrease in catalytic activity. Moreover, combined with electron paramagnetic resonance spectroscopy, a plausible photocatalytic mechanism was proposed. Benefiting from the similarity of lanthanide series, our strategy is expected to apply for the synthesis of lanthanide-based MOF nanosheets as highly efficient catalysts.

    Three-dimensional Porous Sn-Zn Alloy Towards Uniform Zn Plating/stripping
    FAN Xiaoyong, ZHU Yongqiang, WU Yan, ZHANG Shuai, XU Lei, GOU Lei, LI Donglin
    2022, 43(4):  20210861.  doi:10.7503/cjcu20210861
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    A unique three-dimensional(3D) porous Zn-Sn alloy electrode was conducted by electrodepositing Sn-Zn alloy on the 3D porous Cu formed from electroless plating to issue the dendrites growth and corrosion of Zn-based electrodes. The 3D porous structure with high stability and suitable pore size of about 5 μm can reduce the local current density and provide uniform current distribution, thus induce uniform growth of zinc and reduce the formation of rough dendrites. The element Sn in this alloy can enhance the anticorrosion behavior through increasing the over- potential of hydrogen evolution, simultaneously induce uniform Zn deposition with less dendrite through decreasing the Zn nucleation energy barrier and providing abundant Zn nucleation sites. The symmetrical cell using two identical 3D porous Sn-Zn electrodes stably cycle for more than 1200 h with a small voltage hysteresis of 21.3 mV at 0.5 mA/cm2. In contrast, the symmetrical cell assembled using zinc foil(2D Zn) appears obvious voltage fluctuation after cycling for 300 h with a larger voltage hysteresis of 99.2 mV. The full cell is stable up to 2000 cycles at 1.8 A/g current.

    Comparative Effects of Mono/disaccharides on Conjugated Linoleic Acid Vesicles at Near Neutral pH
    LI Lei, FANG Yun, XIA Yongmei, BO Chunling, FAN Ye
    2022, 43(4):  20210860.  doi:10.7503/cjcu20210860
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    Effects of three disaccharides such as lactose and three monosaccharides such as ribose and their mixtures on the formation of fatty acid vesicles(FAV) of conjugated linoleic acid(CLA) in the near-neutral pH range were compared. The pH windows of FAV and phase regions were determined by laser Tyndall effect, the morphology and size of FAV were characterized by transmission electron microscopy and dynamic light scattering, the stabilities of FAV were studied by turbidimetry, the weak non-covalent binding of various saccharides and their mixtures on the FAV surface was proved by isothermal titration calorimetry, and the binding energies were calculated theoretically. The experimental and computational results show that all saccharides and their mixtures can both-side extend the pH window of FAV, and the near neutral-side pH window extends in the following order: disaccharide < monosaccharide ≈ disaccharide/monosaccharide ≤ monosaccharide/monosaccharide. It mainly comes down to the stronger compe-titive adsorption of monosaccharides than disaccharides on the FAV surface. Additionally, the possible multi-binding site adsorption of disaccharides on FAV surface may result in weaker association between the free hydroxyl groups of disaccharides and environmental water molecules than monosaccharides, which makes negative contribution to the enhanced hydrophilicity of the FAV surface relying on polyhydroxyl groups of small molecules.

    Extent and Changeable Rule of HOMO and LUMO Energy of Organic Semiconductors in Nonequilibrium States and a Phenomenological Understanding for the Formation of “Hot Excitons” in OLED
    WANG Jianqiao, MA Yuguang
    2022, 43(4):  20210856.  doi:10.7503/cjcu20210856
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    Based on Nernst equation, the change of electrode potential of organic semiconductor materials was calculated through the relationship between current density and redox species activity, i.e., the change of carrier concentration, so as to establish the mathematical relationship between the energy displacement of their front-line orbit, the highest occupied molecular orbital(HOMO) energy level and the lowest unoccupied molecular orbital (LUMO) energy level relative to the thermodynamic equilibrium state with the current density. Moreover, through the energy gap change caused by the energy level energy displacement, the generation mechanism of thermal exciton in OLED was proposed.

    Study on Preparation and Accessibility of Hierarchical Porous Carbon Supported Platinum Catalyst
    LUO Bian, ZHOU Fen, PAN Mu
    2022, 43(4):  20210853.  doi:10.7503/cjcu20210853
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    In last decade, hierarchical porous carbon has been one of the choices of platinum-based catalysts supports for oxygen reduction. A simple rotating disk electrode(RDE) proves that this type of catalyst exhibits excellent oxygen reduction activity, but almost all of them lack membrane electrodes(MEA) verification, and the performance practicability cannot be guaranteed. In this paper, a polyaniline-based hierarchical porous carbon(NHPC) platinum-supported catalyst(Pt/NHPC850) was designed and prepared. Taking this as an example, the oxygen reduction activity, MEA proton transport and oxygen transport were studied in detail characteristics. RDE test research shows that the specific activity of Pt/NHPC850 catalyst at low I/C(mass ratio of ionomer to carbon support) is lower than that of solid carbon supported Pt catalyst(Pt/XC-72). However, when the I/C increases to the same level as the membrane electrode, the specific activity of Pt/NHPC850 catalyst is better than that of Pt/XC-72 due to the enhanced poisoning effect of Nafion resin on the Pt catalyst. The high Pt dispersibility of Pt/NHPC850 catalyst and its excellent resistance to Nafion poisoning make its mass activity at an I/C of 0.8 to be 1.34 times that of Pt/XC-72 catalyst. The proton transport study of MEA shows that even under high humidification, the proton resistivity of Pt/NHPC850 is 72.6 mΩ·cm2, which is three times that of Pt/XC-72. The polarization curve of the membrane electrode prepared by Pt/NHPC850 declines rapidly at a current density of 500 mA/cm2. The oxygen gain voltage of Pt/NHPC850 reaches 144.4 mV, which is 56.7 mV higher than Pt/XC-72, indicating that the Pt/NHPC850 membrane electrode presents poor oxygen transport performance. The RDE and MEA evaluations of the Pt/NHPC850 catalyst show that although the platinum-carbon catalyst with hierarchical porous carbon as support has improved resistance to Nafion poisoning, it has poor transport properties for protons and oxygen. This type of hierarchical porous carbon needs to be further optimized to meet the application requirements of low platinum polymer exchange membrane fuel cells(PEMFCs).

    Interaction Between Produced Radicals During Ethylene Combustion and Nitrogen Molecules Based on Reaxff Molecular Dynamics Simulation
    LIU Jiaxin, MIN Jie, XU Huajie, REN Haisheng, TAN Ningxin
    2022, 43(4):  20210834.  doi:10.7503/cjcu20210834
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    The combustion of C2H4 in air and the interaction between produced radicals during combustion and nitrogen molecules were studied using reactive force field molecule dynamics(ReaxFF-MD) method under fuel-rich condition at 3200 K. The key information, including the reaction path of ethylene combustion, the reactions of produced radicals during combustion with N2, and formation paths of NO, were obtained by combining reaction networks extracted by ReacNetGenerator program with the related reactions obtained though the code developed by our group. The results showed that the combustion path of ethylene is consistent with that obtained by previous kinetic simulation using those reaction mechanisms of ethylene combustion, indicating that the ReaxFF-MD method is effective and reliable to simulate the high temperature combustion of ethylene. For fuel-rich flame of ethylene, it has been suggested that the CH, C2H, C2and C2O radicals could become important in prompt NO. The reactions of these radicals with N2 and formation paths of NO can provide important clues for the construction of reaction mechanism of nitrogen oxide emission during the combustion of ethylene and larger hydrocarbons.

    Points of Zero Charge and Surface Acid-base Reaction Equilibrium Constants of Mg-Al-Ti Layered Double Hydroxides
    TIAN Zhen, DU Na, LI Haiping, SONG Shue, HOU Wanguo
    2022, 43(4):  20210833.  doi:10.7503/cjcu20210833
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    Five Mg-Al-Ti-CO3 layered double hydroxides(LDHs) were synthesized using a coprecipitation method with a constant Mg2+/(Al3++Ti4+) molar ratio of 3.00 but varying Ti4+/(Al3++Ti4+) molar ratio(RTi, 0—0.40). Their structural charge density(σst), point of zero net charge(pHPZNC), and point of zero net proton charge(pHPZNPC) were determined using potentiometric, salt and potentiometric mass titrations, and their intrinsic equilibrium constants of surface acid-base reactions(pK, pKa1int and pKa2int) were estimated in turn based on the general 1-pK and 2-pK models. Special emphasis was placed on the effect of RTi on their crystal structure and interface electrochemical(IEC) properties. With an increase in RTi, the cell constants(ab and c) and d-spacing increase, arising from the strong electrostatic repulsion between Ti4+ ions. An increase tendency was also observed for pHPZNC, pHPZNPC, pK, pKa1int, and pKa2int with the increase of RTi, indicating a decrease in the deprotonation tendency of surface hydroxyl groups. In addition, it was observed that pHPZNPC is lower than pHPZNC and increases with increasing the electrolyte(NaNO3) concentration, arising from the effect of structural charges. This work provides a better understanding for the IEC properties of Ti4+-containing LDHs.

    Mechanism of Inhibition of Glucose and Proton Cotransport Protein GlcPSe by Cytochalasin B
    ZENG Xianyang, ZHAO Xi, HUANG Xuri
    2022, 43(4):  20210822.  doi:10.7503/cjcu20210822
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    Two protonated states of glucose/H+ symporter with cytochalasin B were simulated by means of molecular dynamics experiments. It was concluded that cytochalasin B has a better inhibitory effect on glucose transporter proteins in the deprotonation phase. It was found that tryptophan 357 and proline 117 are key amino acids for glucose transporter protein binding to cytochalasin B. Not only that, but when the inhibitor acts, the relative position of tryptophan 357 located on the TM10 to cytochalasin B is important for the binding of the inhibitor. These new findings provide a molecular basis for the understanding of the mechanism of glucose-proton cotransport protein inhibition and the development of drug targets for it.

    Catalytic Methane Combustion over CeO2 Supported PdO and Ce1‒x Pd x O2‒δ Species
    WANG Mingzhi, ZHENG Yanping, WENG Weizheng
    2022, 43(4):  20210816.  doi:10.7503/cjcu20210816
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    Pd/CeO2 catalysts containing mainly PdO and Ce1?x Pd x O2?δ species were prepared by modulating the deposition method of Pd species on CeO2. The Raman and XPS characterizations of the catalysts confirmed the presence of these two types of Pd species on the prepared catalysts. The characterization results of O2-TPD and H2-TPR showed that the Ce1?x Pd x O2?δ species with stronger interactions with CeO2 featured more stronger Pd—O bonds compared to the PdO species. The results of catalytic performance testing for the CH4 combustion reaction showed that, the Pd/CeO2 catalyst dominated with PdO species showed a good activity during the light off process with a T10 and T90 of 275 and 367 ℃, respectively, at a feed gas ratio of 1%CH4-4%O2-Ar and gaseous hourly space velocity(GHSV) of 60000 mL·gcat-1·h?1, while the catalysts dominated with Ce1?x Pd x O2?δ species possessed poor activity with T10 in excess of 420 ℃ under the same condition. The CH4-TPR characterization of the catalysts showed that the catalytic activity started to increase only when the PdO or Ce1?x Pd x O2?δ species started to be reduced by CH4 during the light off process. For the PdO species, the relatively weak Pd—O bonding allows the lattice oxygen on the Pd species to participate in the oxidation of CH4 at lower temperatures, and CeO2 support contributes to the reoxidation of the PdO x through oxygen migration, which in turn completes the process of catalysis by PdO/Pd0 cycle. The low activity of the ionic Ce1?x Pd x O2?δ should attribute to its strong Pd—O—Ce linkages which are difficult to be reduced by CH4 during the reaction. Furthermore, we prepared Pd/γ-Al2O3 catalysts by the same method using γ-Al2O3 as the support, and the characterization results further confirmed that the PdO species with weaker interaction with γ-Al2O3 are more easily be reduced by CH4 and thus exhibit better catalytic activity. It can be concluded that the reducibility of the oxidized Pd species on Pd/CeO2 by CH4 is one of the important factors determining the activity of the catalyst for the methane combustion reaction.

    Influence of Different Transition Metal Decoration on the Propane Dehydrogenation Performance over Pt/M-DMSN Catalysts
    HU Huimin, CUI Jing, LIU Dandan, SONG Jiaxin, ZHANG Ning, FAN Xiaoqiang, ZHAO Zhen, KONG Lian, XIAO Xia, XIE Zean
    2022, 43(4):  20210815.  doi:10.7503/cjcu20210815
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    A series of transition metal modified dendritic mesoporous silica nanoparticles(DMSN) supported Pt(Pt/M-DMSN, M=Fe, Co, Ni, Cu, Zn) catalysts were prepared by a two-step method. And their catalytic performances were tested for propane dehydrogenation. The XRD, TEM, UV-Vis DRS and H2-TPR characterizations results indicate the different dispersion state of transition metal on DMSN surface and the different interaction of the transition metal and Pt. Zn-DMSN support shows the most favorable dispersion to Pt, and the lowest coke deposition on the corresponding spent catalyst. Pt/Fe-DMSN catalysts show strong Pt-support interaction. According to the activity test results, Pt/Fe-DMSN catalyst shows the best performance for propane dehydrogenation with the propane initial conversion of 44.2%. And the propane conversion is 36.5% after 6 h reaction.

    Planar Pentacoordinate Silicon and Germanium in XBe5H6(X=Si, Ge) Clusters
    GUO Jinchang, LIU Fanglin
    2022, 43(4):  20210807.  doi:10.7503/cjcu20210807
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    Computational design of ternary XBe5H6(X=Si, Ge) clusters was reported, which were global-minimum structures on the potential energy surfaces, featuring planar pentacoordinate silicon/germanium(ppSi/Ge). XBe5H6 (X=Si, Ge) clusters have the perfect fan-shaped structures: Si/Ge atoms are coordinated by five Be atoms; four H atoms are bonded to Be atoms in bridge mode, and the remaining two H atoms are bonded to Be atoms at both ends. Chemical bonding analyses reveal that the ppSi/Ge core is governed by delocalized 2π/6σ bonding, that is, double π/σ aromaticity, which also makes the Si/Ge atom conform to the octet rule. Additional twelve electrons are contributed to peripheral Be—H—Be and Be—H σ bonding. Energy decomposition analysis-Natural orbital for chemical valence(EDA-NOCV) analyses indicate that there is mainly electron-sharing bonding between the Si/Ge and Be5H6 ligands.

    Polymer Chemistry
    Quantifying the Degree of Weakening Effect of Nonpolar Organic Solvent on the Strength of Intramolecular Hydrogen Bonding by Single-molecule Force Spectroscopy
    ZHANG Yong, XU Jun, BAO Yu, CUI Shuxun
    2022, 43(4):  20210863.  doi:10.7503/cjcu20210863
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    The influence degree of nonpolar organic solvents on the strength of intramolecular hydrogen bonding (H-bond) have been quantitatively studied by taking three kinds of polyvinyl alcohol(PVA) with different alcoholysis degrees as the model system in this paper. The single-molecule force spectroscopy(SMFS) results show that the strengths of intramolecular H-bonds in three kinds of PVA in nonpolar organic solvents are ca.48% of those in vacuum. These findings indicate that the nonpolar organic solvent has a significant weakening effect on the intramole-cular H-bond, which can weaken its strength by ca.50%. This study suggests that the influence of liquid environments on the strengths of non-covalent interactions and the single-chain elasticities of polymers should be reconsi-dered.

    Synthesis and Characterization of Phenothiazine-based Schiff Bases as Visible Light Photoinitiators
    XU Dandan, ZOU Xiucheng, LUO Jing, LIU Ren
    2022, 43(4):  20210857.  doi:10.7503/cjcu20210857
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    In order to construct photoinitiators with strong molar extinction coefficient in the visible light region, four novel D-π-A type phenothiazine-based derivatives have been designed and synthesized. The structures were cha-racterized by nuclear magnetic resonance and high-resolution mass spectrum. These phenothiazine derivatives, as a strong electron-donating group, can easily undergo photo-induced electron transfer with iodonium salt(Iod), thereby initiating the radical and cationic photopolymerization. Interestingly, the prepared photoinitiators exhibit the characteristics of charge transfer in the ground and excited states and have the strong molar extinction coefficient of 104 L·mol-1·cm-1 in the spectral range of 350—450 nm, and have the red shifts about 50 nm compared with the commercial photoinitiator 2-isopropylthioxanthone(ITX), well matching the emitting spectra of the popularly used 405 nm LED light source. Theoretical calculations of molecular orbitals also explain the excellent optical properties of photoinitiators. The two-component initiating system has faster initiation efficiency and higher conversion rate than that of commercial photoinitiator ITX/Iod for free radical as well as cation photopolymerizations by changing different conditions of the formulas. The formula with PI(0.2%, molar fraction) and Iod(2%, molar fraction) exhibit the best curing effect. An photoinduced electron transfer(PET) mechanism was established based on steady-state photolysis experiments, and electron spin resonance spectroscopy experiment which captured the benzene radicals. The free energy changes(ΔGet) were measured by cyclic voltammetry(CV) experiments which proved the possibility of PET mechanism thermodynamically. Under irradiation, APN/Iod undergo the electronic transfer and the formed benzene radicals initiate polymerization of acrylates, and the active species is produced to initiate cationic polymerization of epoxy at the same time. In addition, the printing of fluorescent light-emitting devices was successfully carried out through the technology of Digital Light Processing(DLP) 3D printing.

    Preparation and Properties of Gold Nanocages/Hyaluronic Acid Core-shell Nanocarriers with pH/Enzyme/ Photothermal Multiple Responses
    FAN Xiaohui, WANG Yang, YANG Yuanyuan, ZHANG Yuhong
    2022, 43(4):  20210855.  doi:10.7503/cjcu20210855
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    The core-shell nano drug loaded particle DOX@AuNC@HA(DAH) was prepared by a simple one pot method using gold nanocage(AuNC) as the core, sulfhydryl modified hyaluronic acid(LC-HA) as the shell and doxorubicin hydrochloride(DOX) as the drug model. The gold nanocage provides a container for drug loading and endows the carrier with photothermal properties. The modified hyaluronic acid encapsulates the gold nanocage and provides pH/enzyme response and targeted mediating functions. The structure of DAH was characterized, and the drug loading, controlled release performances, cell uptake and cytotoxicity were studied. The results show that the DAH nanoparticles with the core-shell structures have a high drug loading capacity, a good cycle stability and excellent photothermal conversion efficiency under the irradiation of laser source. In phosphate buffer solution with a pH of 7.4, DAH has high stability, the DOX leakage ratio in 20 h is less than 20%; and DAH exhibits good stimulus response and can release the loaded drug quickly in acidic, hyaluronidase and photothermal action environment. In addition, DAH is more easily uptaken by tumor cells in cell experiments, which demonstrates certain targeting, showing better stimulus responsiveness. When chemotherapy and photothermal therapy works together, the activity of tumor cells is greatly weakened, showing the advantages and potential of combined therapy.

    Synthesis of Phosphaphenanthrene-modified Cardanol-based Polyol and Its Performance as Flame Retardant in Rigid Polyurethane Foams
    TANG Gang, SUN Junjie, ZHANG Dongxin, WU Qiang, ZHANG Hexin, SHEN Haifeng, TAO Yi, LIU Xiuyu
    2022, 43(4):  20210847.  doi:10.7503/cjcu20210847
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    A phosphaphenanthrene-modified cardanol-based polyol(P-Cardanol-Polyol) was synthesized from car-danol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO), and its structure was characterized by 1H and 31P nuclear magnetic resonance(NMR) spectra. Subsequently, P-Cardanol-Polyol was used to prepare a series of flame-retardant rigid polyurethane foams(RPUFs). The effects of P-Cardanol-Polyol on the morphology, density, thermal conductivity, compression property, thermal stability and flame-retardant properties of RPUFs were investigated. The results showed that P-Cardanol-Polyol had a negligible effect on the density of RPUFs; with the increased amount of P-Cardanol-Polyol, the average pore size and the thermal conductivity of flame-retardant RPUFs decreased gradually. The maximum heat release rate and total heat release of the unmodified RPUF were 390 kW/m2 and 31.9 MJ/m2, respectively, while those of flame-retardant RPUF were reduced to 340 kW/m2 and 24.6 MJ/m2. In addition, the compressive strength of flame-retardant RPUF was about 13% higher than that of unmodified RPUF. The results of char analysis showed that P-Cardanol-Polyol can promote the formation of a continuous and dense char layer with good thermal-oxidative resistance, which is conducive to reducing the escape of combustible gases during combustion, so as to improve the flame-retardant performance.

    Three-dimensional Printing of Photocrosslinked Self-supporting Silk Fibroin Hydrogels
    HUANG Yi, LYU Lingling, PAN Xiaopeng, SUN Guangdong, LI Yongqiang, YAO Juming, SHAO Jianzhong
    2022, 43(4):  20210841.  doi:10.7503/cjcu20210841
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    As a biological macromolecular material degummed from silk fiber, silk fibroin(SF) is considered to be an ideal candidate for bioink components in three-dimensional(3D) bioprinting because of its excellent biocompatibility, biodegradability and tunable mechanical properties. However, the conventional silk fibroin crosslinking methods cannot meet the requirements of 3D printing on the real-time forming efficiency and biocompatibility. In order to realize the 3D rapid prototyping of silk fibroin, the in-situ photocrosslinking processing technology of self-supporting silk fibroin hydrogel was proposed by combining the blue light-induced self-crosslinking method with 3D extruded printing technology. The basic rheological properties, photocrosslinking properties and moulding processability of silk fibroin solution were studied by using rotary rheometer, photorheological test system and modified 3D extruded printing equipment. The results showed that the silk fibroin solution(<20%, mass fraction) was mainly characterized by viscidity, and its inadequate structural strength and stability cannot meet the requirements of 3D extruded printing for material formability, shape retention and printing accuracy. Rapid photocrosslinking molding processing of silk fibroin hydrogel can be achieved by light-induced self-crosslinking in the presence of tris(2,2-bipyridyl) ruthenium(II) chloride hexahydrate[Ru(Ⅱ)] and potassium persulfate(KPS) as blue light initiators. Tyrosine residues on adjacent SF macromolecular chains can be oxidized into tyrosine free radicals under the action of excited active species, and then coupled and crosslinked into di-tyrosine structure. Photocrosslinking behavior of silk fibroin under blue light irradiation conformed to exponential growth model. Due to the “filter effect” of the photosensitizer on the incident light, silk fibroin solution showed the optimized photocrosslinking performance when the dose of the photosensitizer Ru(Ⅱ) was 0.05 mmol/L. By further adjusting the parameters such as air pressure, needle aperture, moving speed and curing rate, semi-transparent and micro-elastic silk fibroin hydrogel can be printed in real time by 3D extruded printing equipment under continuous blue light irradiation. The efficient and accurate construction of silk fibroin gel materials from single-layer geometric structure to multi-layer three-dimensional network structure can be realized, which provides a new idea for biological 3D printing of self-supporting silk fibroin gel materials.

    Preparation and Performance of Thermally Conductive Expanded Graphite/Polyetherimide Composites
    ZHAO Junyu, WANG Chunbo, WANG Chengyang, ZHANG Ke, CONG Bing, YANG Lan, ZHAO Xiaogang, CHEN Chunhai
    2022, 43(4):  20210800.  doi:10.7503/cjcu20210800
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    Large specific surface area and high thermal conductivity of graphite nanoplatelets(GNP) on expanded graphite(EG) after heat treatment was taken advantage, the crushed EG was used as thermally conductive filler and compounded with polyetherimide(PEI) through ball milling. Then the EG/PEI composites was prepared by thermal lamination, and its microscopic morphology, thermal conductivity and thermal performance were studied. The results show that ball milling treatment can reduce the pores between GNP and GNP and facilitate the uniform mixing of EG and PEI. Hot pressing can induce and promote the arrangement and orientation of GNPs along the horizontal direction, thereby significantly improving the in-plane thermal conductivity of the composite material. When the maaa fraction of EG is 20%, the thermal conductivity of the EG/PEI composite is 2.38 W?m?1?K?1. Compared with pure PEI, the thermal conductivity increases by about 1224%. The prepared EG/PEI composites are all with high thermal stability and storage modulus recovery rate, it is an ideal thermally conductive material with excellent comprehensive performance.