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2021 Volume 40 Issue 11
2021, 40(11): 1411-1422
doi: 10.14102/j.cnki.0254–5861.2011–3191
Abstract:
The cytochrome P411 enzyme is a variant of cytochrome P450BM3 from Bacillus megaterium whose active site is an iron porphyrin imine ([Fe(Por)(NH)]-) specie. This specie has been reported to successfully promote the primary amination of benzylic and allylic C(sp3)-H bonds. We employed density functional theory to study the electronic structure of the active site of P411 enzyme and the primary amination of C-H bond reaction that it catalyzes. The calculated spin densities and orbital values indicate the existence of resonance in this specie; namely, [(por)(–OH)FeⅣ–N2-–H]- ↔ [(por)(–OH)FeⅢ–N•-–H]-. The amination of C(sp3)-H bonds consists of two main reaction steps: hydrogen-atom abstraction and radical recombination, and the former is demonstrated to be the rate-determining step. Furthermore, we studied the regioselectivity of the amination of primary and secondary C(sp3)-H bonds. Our calculations indicated that the secondary C(sp3)-H bonds of the substrate would be more favored for the activation by P411 enzyme. These results provide valuable information for understanding the properties and selectivity of C-H/C-N bond-activation reactions catalyzed by the P411 enzyme or other similar enzymes.
The cytochrome P411 enzyme is a variant of cytochrome P450BM3 from Bacillus megaterium whose active site is an iron porphyrin imine ([Fe(Por)(NH)]-) specie. This specie has been reported to successfully promote the primary amination of benzylic and allylic C(sp3)-H bonds. We employed density functional theory to study the electronic structure of the active site of P411 enzyme and the primary amination of C-H bond reaction that it catalyzes. The calculated spin densities and orbital values indicate the existence of resonance in this specie; namely, [(por)(–OH)FeⅣ–N2-–H]- ↔ [(por)(–OH)FeⅢ–N•-–H]-. The amination of C(sp3)-H bonds consists of two main reaction steps: hydrogen-atom abstraction and radical recombination, and the former is demonstrated to be the rate-determining step. Furthermore, we studied the regioselectivity of the amination of primary and secondary C(sp3)-H bonds. Our calculations indicated that the secondary C(sp3)-H bonds of the substrate would be more favored for the activation by P411 enzyme. These results provide valuable information for understanding the properties and selectivity of C-H/C-N bond-activation reactions catalyzed by the P411 enzyme or other similar enzymes.
2021, 40(11): 1423-1432
doi: 10.14102/j.cnki.0254–5861.2011–3161
Abstract:
Adsorbent has been widely used for the recovery and enrichment of rare metals from waste water. Herein, a graphene-based adsorbent, graphene oxide/Fe3O4 (GO/Fe3O4) nanocomposite, was prepared by a facile hydrothermal method, and characterized by X-ray diffraction, Scanning Electron Microscope, X-ray Photoelectron Spectroscopy, Zeta potential and magnetization. The material has been explored for the recovery of In from simulated waste water. The test results show that the nanocomposite has a reasonable adsorption capacity on indium in a wide pH range, e.g., the adsorption percent and quantity of In(Ⅲ) from the aqueous solutions at pH = 4 and C0 = 50 mg·L−1 are 91% and 43.98 mg·L−1, respectively. In addition, the nanocomposites maintain a 75.5% cycling capacity and a 71% removal efficiency after five continuous cycles due to their novel properties of high specific surface area and superparamagnetism. The pseudo-second-order adsorption model can be used to interpret the kinetic data. High adsorption efficiency and good reusability can make the nanocomposite a promising adsorbent for recovery of In(Ⅲ).
Adsorbent has been widely used for the recovery and enrichment of rare metals from waste water. Herein, a graphene-based adsorbent, graphene oxide/Fe3O4 (GO/Fe3O4) nanocomposite, was prepared by a facile hydrothermal method, and characterized by X-ray diffraction, Scanning Electron Microscope, X-ray Photoelectron Spectroscopy, Zeta potential and magnetization. The material has been explored for the recovery of In from simulated waste water. The test results show that the nanocomposite has a reasonable adsorption capacity on indium in a wide pH range, e.g., the adsorption percent and quantity of In(Ⅲ) from the aqueous solutions at pH = 4 and C0 = 50 mg·L−1 are 91% and 43.98 mg·L−1, respectively. In addition, the nanocomposites maintain a 75.5% cycling capacity and a 71% removal efficiency after five continuous cycles due to their novel properties of high specific surface area and superparamagnetism. The pseudo-second-order adsorption model can be used to interpret the kinetic data. High adsorption efficiency and good reusability can make the nanocomposite a promising adsorbent for recovery of In(Ⅲ).
2021, 40(11): 1433-1438
doi: 10.14102/j.cnki.0254–5861.2011–3181
Abstract:
There are numerous studies on nitrogen-rich heterocycles explosive design and synthesis due to their good detonation activity. A series of bistriazoles with different heterocyclic linkages were designed and calculated by density functional theory (DFT) b3lyp/6-311+G* method. The structure, detonation properties and stability of the energetic compounds have been investigated. According to the results from heats of formation (HOFs), the HOF values of bistriazole with heterocycle linkage (M1~M4) are higher than those of the corresponding diamino-heterocycle bridged ones (M5~M8). By analyzing the bond dissociation energy (BDE), -NH- is not conducive to increase the stability of the derivatives. In terms of detonation performances and stability of bistriazole derivatives, the combination of furazan or tetrazole linkages with bis-triazoles may be considered as potential candidates for energetic materials.
There are numerous studies on nitrogen-rich heterocycles explosive design and synthesis due to their good detonation activity. A series of bistriazoles with different heterocyclic linkages were designed and calculated by density functional theory (DFT) b3lyp/6-311+G* method. The structure, detonation properties and stability of the energetic compounds have been investigated. According to the results from heats of formation (HOFs), the HOF values of bistriazole with heterocycle linkage (M1~M4) are higher than those of the corresponding diamino-heterocycle bridged ones (M5~M8). By analyzing the bond dissociation energy (BDE), -NH- is not conducive to increase the stability of the derivatives. In terms of detonation performances and stability of bistriazole derivatives, the combination of furazan or tetrazole linkages with bis-triazoles may be considered as potential candidates for energetic materials.
2021, 40(11): 1439-1448
doi: 10.14102/j.cnki.0254–5861.2011–3194
Abstract:
Two isostructural tellurite phosphates Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn) have been synthesized via hydrothermal method. Both of them crystalize in monoclinic space group C2/m (No. 12). For Ni2ZnTe2ⅣO2(PO4)2(OH)4, a = 19.3247(10), b = 5.9697(3), c = 4.7737(2) Å, β = 103.637(5)°, V = 535.18(5) Å3, Z = 2, Mr = 727.94, S = 1.103, Dc = 4.517 g·cm−3, μ(MoKα) = 11.434 mm–1 and F(000) = 672, the final R = 0.0369 and wR = 0.1086 for 639 observed reflections with I > 2σ(I). The crystal structure of Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn) features a 3D framework composed of [Ni2O2(PO4)2]6− layers interconnected by [MTe2O2(OH)4]2+ single chains. Different magnetic susceptibility results at low temperature of the two title compounds confirm that Zn(1) completely occupies the Ni(2) position but not partially substitutes both Ni(1) and Ni(2) position atoms. Additionally, the acentric TeO3(OH)2 tetragonal pyramids are aligned in an antiparallel manner, resulting in the crystallization of centrosymmetric (C2/m) crystal structure instead of the non-centrosymmetric crystal structure. The investigation of the origin of centrosymmetric crystal structure with strong dipole moment units provides deeper understanding for future rational design for non-centrosymmetric crystal structure.
Two isostructural tellurite phosphates Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn) have been synthesized via hydrothermal method. Both of them crystalize in monoclinic space group C2/m (No. 12). For Ni2ZnTe2ⅣO2(PO4)2(OH)4, a = 19.3247(10), b = 5.9697(3), c = 4.7737(2) Å, β = 103.637(5)°, V = 535.18(5) Å3, Z = 2, Mr = 727.94, S = 1.103, Dc = 4.517 g·cm−3, μ(MoKα) = 11.434 mm–1 and F(000) = 672, the final R = 0.0369 and wR = 0.1086 for 639 observed reflections with I > 2σ(I). The crystal structure of Ni2MⅡTe2ⅣO2(PO4)2(OH)4 (MⅡ = Ni, Zn) features a 3D framework composed of [Ni2O2(PO4)2]6− layers interconnected by [MTe2O2(OH)4]2+ single chains. Different magnetic susceptibility results at low temperature of the two title compounds confirm that Zn(1) completely occupies the Ni(2) position but not partially substitutes both Ni(1) and Ni(2) position atoms. Additionally, the acentric TeO3(OH)2 tetragonal pyramids are aligned in an antiparallel manner, resulting in the crystallization of centrosymmetric (C2/m) crystal structure instead of the non-centrosymmetric crystal structure. The investigation of the origin of centrosymmetric crystal structure with strong dipole moment units provides deeper understanding for future rational design for non-centrosymmetric crystal structure.
2021, 40(11): 1449-1455
doi: 10.14102/j.cnki.0254–5861.2011–3156
Abstract:
A new POM-based coordination polymer, [Cl2Cu11Ⅰ(trz)8][H3SiW12O40] (1), was successfully obtained under hydrothermal reaction. The compound was characterized by single-crystal X-ray diffraction, TG analyses, IR spectra and PXRD analysis. Compound 1 shows extreme stability and outstanding catalytic activity to the degradation of organic dye pollutant.
A new POM-based coordination polymer, [Cl2Cu11Ⅰ(trz)8][H3SiW12O40] (1), was successfully obtained under hydrothermal reaction. The compound was characterized by single-crystal X-ray diffraction, TG analyses, IR spectra and PXRD analysis. Compound 1 shows extreme stability and outstanding catalytic activity to the degradation of organic dye pollutant.
2021, 40(11): 1456-1460
doi: 10.14102/j.cnki.0254–5861.2011–3180
Abstract:
A new two-dimensional (2D) bio-metal-organic framework based on trinuclear cluster units, [Zn3(adeninate)2(CH3COO)4]∙DMF (Zn–A), was synthesized by the self-assembly of biomolecule adenines with zinc ions. Topological analysis reveals its 44 connected layer structure. Remarkably, Zn–A bears high sensitivity and selectivity detection ability of iron ion with the limit of detection being 4.0 × 10-6 mol/L.
A new two-dimensional (2D) bio-metal-organic framework based on trinuclear cluster units, [Zn3(adeninate)2(CH3COO)4]∙DMF (Zn–A), was synthesized by the self-assembly of biomolecule adenines with zinc ions. Topological analysis reveals its 44 connected layer structure. Remarkably, Zn–A bears high sensitivity and selectivity detection ability of iron ion with the limit of detection being 4.0 × 10-6 mol/L.
2021, 40(11): 1461-1468
doi: 10.14102/j.cnki.0254–5861.2011–3182
Abstract:
By solvothermal reaction of Cd(Ⅱ) with organic ligand N, N΄-bis(3, 5-dicarboxylphenyl)-thiophene-2, 5-dicarboxamide (H4L), a water-stable complex [Cd4(H2L)4(H2O)10]·2CH3OH·8H2O·4DMF (1, C102H120Cd4N12O64S4) has been successfully synthetized (DMF = N, N-dimethylformamide). 1 crystallizes in the triclinic space group of P\begin{document}$ \overline 1 $\end{document}
By solvothermal reaction of Cd(Ⅱ) with organic ligand N, N΄-bis(3, 5-dicarboxylphenyl)-thiophene-2, 5-dicarboxamide (H4L), a water-stable complex [Cd4(H2L)4(H2O)10]·2CH3OH·8H2O·4DMF (1, C102H120Cd4N12O64S4) has been successfully synthetized (DMF = N, N-dimethylformamide). 1 crystallizes in the triclinic space group of P
2021, 40(11): 1469-1474
doi: 10.14102/j.cnki.0254–5861.2011–3186
Abstract:
One new Mn(Ⅱ) coordination polymer, [Mn(Htia)2(H2O)2]n·2nH2O (1, H2tia = 4-(1, 2, 4-triazol-1-yl)isophthalic acid) has been synthesized in mixed solvents under solvothermal conditions. Further characterizations including single-crystal XRD, elemental analysis, IR spectroscopy, thermogravimetric analysis and powder XRD were performed to verify the structure. Complex 1 displays a one-dimensional (1D) chain and is similar to a reported Mn(Ⅱ) complex 2 {[Mn(Htta)2(H2O)2]·2H2O}n. It crystallizes in triclinic P\begin{document}$ \overline 1 $\end{document}
One new Mn(Ⅱ) coordination polymer, [Mn(Htia)2(H2O)2]n·2nH2O (1, H2tia = 4-(1, 2, 4-triazol-1-yl)isophthalic acid) has been synthesized in mixed solvents under solvothermal conditions. Further characterizations including single-crystal XRD, elemental analysis, IR spectroscopy, thermogravimetric analysis and powder XRD were performed to verify the structure. Complex 1 displays a one-dimensional (1D) chain and is similar to a reported Mn(Ⅱ) complex 2 {[Mn(Htta)2(H2O)2]·2H2O}n. It crystallizes in triclinic P
2021, 40(11): 1475-1481
doi: 10.14102/j.cnki.0254-5861.2011-3190
Abstract:
A CeⅢ linear complex of N-hydroxy-1, 8-naphthalenedicarboximide (HL) has been synthesized with acenaphthoquinone dioxime (acndH2) under solvothermal conditions, in which L is generated by a series of in-situ reactions starting from acndH2. X-ray crystallography reveals the coordination chains of CeⅢ ions are assembled into a 3D supramolecular framework via π…π interactions. The title complex has been characterized by IR and UV-Vis spectra and thermogravimetric analysis (TGA). Furthermore, the fluorescent properties study demonstrated a ligand-based emission of the CeⅢ complex with ~6 nm blue-shift compared with the emisision of the HL ligand.
A CeⅢ linear complex of N-hydroxy-1, 8-naphthalenedicarboximide (HL) has been synthesized with acenaphthoquinone dioxime (acndH2) under solvothermal conditions, in which L is generated by a series of in-situ reactions starting from acndH2. X-ray crystallography reveals the coordination chains of CeⅢ ions are assembled into a 3D supramolecular framework via π…π interactions. The title complex has been characterized by IR and UV-Vis spectra and thermogravimetric analysis (TGA). Furthermore, the fluorescent properties study demonstrated a ligand-based emission of the CeⅢ complex with ~6 nm blue-shift compared with the emisision of the HL ligand.
2021, 40(11): 1482-1488
doi: 10.14102/j.cnki.0254-5861.2011-3195
Abstract:
A new Pb(Ⅱ) coordination polymer, [Pb(adip)(L)2]n (1, H2adip = adipic acid, L = 2-(4-N, N΄-dimethylphenyl)-1-H-imidazo[4, 5-f][1,10] phenanthroline), was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, FT-IR, thermogravimetric, fluorescence spectrum and elemental analysis techniques. Complex 1 crystallizes in triclinic system, space group P\begin{document}$ \overline 1 $\end{document}
A new Pb(Ⅱ) coordination polymer, [Pb(adip)(L)2]n (1, H2adip = adipic acid, L = 2-(4-N, N΄-dimethylphenyl)-1-H-imidazo[4, 5-f][1,10] phenanthroline), was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, FT-IR, thermogravimetric, fluorescence spectrum and elemental analysis techniques. Complex 1 crystallizes in triclinic system, space group P
2021, 40(11): 1489-1495
doi: 10.14102/j.cnki.0254-5861.2011-3197
Abstract:
A new tetranuclear cuprous halide complex, (CuBr)4(PN)2 (PN = 2-(diphenylphosphaneyl)-6-methoxypyridine), was synthesized and fully characterized. In solid state, this complex exhibits efficient blue emission with a photoluminescence quantum yield of 43.3% and a decay time of 19 μs at room temperature. The theoretical calculations, combined with the temperature dependence of spectroscopic properties and emission decay behaviors, indicate that the emission in the solid state originates from the 1, 3(MLCT + XLCT) excited states, which are in thermal equilibrium with a small energy gap of about 0.1 eV.
A new tetranuclear cuprous halide complex, (CuBr)4(PN)2 (PN = 2-(diphenylphosphaneyl)-6-methoxypyridine), was synthesized and fully characterized. In solid state, this complex exhibits efficient blue emission with a photoluminescence quantum yield of 43.3% and a decay time of 19 μs at room temperature. The theoretical calculations, combined with the temperature dependence of spectroscopic properties and emission decay behaviors, indicate that the emission in the solid state originates from the 1, 3(MLCT + XLCT) excited states, which are in thermal equilibrium with a small energy gap of about 0.1 eV.
2021, 40(11): 1496-1504
doi: 10.14102/j.cnki.0254-5861.2011-3183
Abstract:
Controlled stacking of different two-dimensional (2D) atomic layers hold great promise for significantly optimizing the optical properties of 2D materials and broadening their applications. Here, vertical 2D MoS2/Bi2Te3 heterostructures with high crystallinity and optical quality have been successfully constructed, through drop-casting 2D Bi2Te3 flakes on chemical vapor deposition (CVD)-grown MoS2 flakes. Based on our homebuilt micro Z-scan and pump-probe measurement, we precisely investigated and compared the nonlinear optical (NLO) performance of an individual micro-sized MoS2 flake before and after stacking 2D Bi2Te3 nanoplates. Moreover, layer-dependent ultrafast carrier dynamics of CVD-grown MoS2 flakes were also explored. Owing to the efficient charge transfer from the monolayer (1 L) MoS2 to 2D Bi2Te3, the 1L MoS2/Bi2Te3 heterostructure demonstrated excellent NLO performance with superior nonlinear saturable absorption coefficient and ultrashort carrier lifetime. Our work greatly enriches our understanding of 2D heterostructure and paves the way for designing new type of tunable 2D photonics materials by combining the optical advantages of different 2D materials.
Controlled stacking of different two-dimensional (2D) atomic layers hold great promise for significantly optimizing the optical properties of 2D materials and broadening their applications. Here, vertical 2D MoS2/Bi2Te3 heterostructures with high crystallinity and optical quality have been successfully constructed, through drop-casting 2D Bi2Te3 flakes on chemical vapor deposition (CVD)-grown MoS2 flakes. Based on our homebuilt micro Z-scan and pump-probe measurement, we precisely investigated and compared the nonlinear optical (NLO) performance of an individual micro-sized MoS2 flake before and after stacking 2D Bi2Te3 nanoplates. Moreover, layer-dependent ultrafast carrier dynamics of CVD-grown MoS2 flakes were also explored. Owing to the efficient charge transfer from the monolayer (1 L) MoS2 to 2D Bi2Te3, the 1L MoS2/Bi2Te3 heterostructure demonstrated excellent NLO performance with superior nonlinear saturable absorption coefficient and ultrashort carrier lifetime. Our work greatly enriches our understanding of 2D heterostructure and paves the way for designing new type of tunable 2D photonics materials by combining the optical advantages of different 2D materials.
2021, 40(11): 1505-1512
doi: 10.14102/j.cnki.0254-5861.2011-3162
Abstract:
Photoelectrochemistry that use semiconductors to absorb sunlight for water splitting provides an effective method for the development of renewable hydrogen energy in the future. In this paper, a transparent and highly-efficient cobalt-iron oxide (Co3FeOx) nano-film was fabricated through hydrothermal method by directional adjustment of atomic ratio to promote the kinetics of BiVO4 (BVO) photoanode water oxidation. As a result, the Co3FeOx-modified BVO photoanode (Co3FeOx/BVO) exhibits an impressive photocurrent density of 4.0 mA·cm-2 at 1.23 V versus reversible hydrogen electrode (RHE), approximately 2.17-fold higher than that of bare BVO, as well as a cathodically shifted onset potential of 320 mV. Transparent catalyst nanolayer structure is clarified by ultraviolet-visible spectroscopy. In addition, the Co3FeOx/BVO photoanode has better stability, and there is no obvious activity degradation after 10 hours of reaction. This strategy provides a broad prospect for the use of water oxidation co-catalyst to achieve effective water splitting.
Photoelectrochemistry that use semiconductors to absorb sunlight for water splitting provides an effective method for the development of renewable hydrogen energy in the future. In this paper, a transparent and highly-efficient cobalt-iron oxide (Co3FeOx) nano-film was fabricated through hydrothermal method by directional adjustment of atomic ratio to promote the kinetics of BiVO4 (BVO) photoanode water oxidation. As a result, the Co3FeOx-modified BVO photoanode (Co3FeOx/BVO) exhibits an impressive photocurrent density of 4.0 mA·cm-2 at 1.23 V versus reversible hydrogen electrode (RHE), approximately 2.17-fold higher than that of bare BVO, as well as a cathodically shifted onset potential of 320 mV. Transparent catalyst nanolayer structure is clarified by ultraviolet-visible spectroscopy. In addition, the Co3FeOx/BVO photoanode has better stability, and there is no obvious activity degradation after 10 hours of reaction. This strategy provides a broad prospect for the use of water oxidation co-catalyst to achieve effective water splitting.
2021, 40(11): 1513-1524
doi: 10.14102/j.cnki.0254-5861.2011-3189
Abstract:
In situ growth of carbon nanomaterials on active substance is a very favorable strategy for the preparation of electrode in lithium-ion batteries with excellent electrochemical performance and high stability. Small-sized TiO2 nanoparticles intercalated into carbon nanosheets (CNS@TiO2SNP-600) were successfully synthesized via in-situ polymerization-carbonization method, utilizing layered H2Ti4O9 (HTO) as template and benzidine as carbon source. The morphology and size of TiO2 are greatly influenced by carbonization temperature. The coin cell with the CNS@TiO2SNP-600 electrode demonstrates a discharge specific capacity of 430.4 mAh⋅g-1 at a current density of 0.1 A⋅g-1, and the capacity retention rate is 88.1% after 100 cycles; and it also displays a high discharge specific capacity of 101.8 mAh⋅g-1 at a high current density of 12.8 A⋅g-1. The excellent electrochemical performances can be ascribed to the capacitance effect originated from the intercalated structure of in-situ grown CNS and TiO2 nanoparticles. We believe this type of materials can be widely used in the lithium-ion batteries and other related green chemical fields.
In situ growth of carbon nanomaterials on active substance is a very favorable strategy for the preparation of electrode in lithium-ion batteries with excellent electrochemical performance and high stability. Small-sized TiO2 nanoparticles intercalated into carbon nanosheets (CNS@TiO2SNP-600) were successfully synthesized via in-situ polymerization-carbonization method, utilizing layered H2Ti4O9 (HTO) as template and benzidine as carbon source. The morphology and size of TiO2 are greatly influenced by carbonization temperature. The coin cell with the CNS@TiO2SNP-600 electrode demonstrates a discharge specific capacity of 430.4 mAh⋅g-1 at a current density of 0.1 A⋅g-1, and the capacity retention rate is 88.1% after 100 cycles; and it also displays a high discharge specific capacity of 101.8 mAh⋅g-1 at a high current density of 12.8 A⋅g-1. The excellent electrochemical performances can be ascribed to the capacitance effect originated from the intercalated structure of in-situ grown CNS and TiO2 nanoparticles. We believe this type of materials can be widely used in the lithium-ion batteries and other related green chemical fields.
2021, 40(11): 1525-1534
doi: 10.14102/j.cnki.0254-5861.2011-3196
Abstract:
Surface hydrophilization is required for numbers of applications such as biosensor, biomedical implants and marine coating. However, the preparation of hydrophilic surface from a solid substrate still suffers from limited thicknesses, complex procedures, restricted substrates and harsh conditions. Herein, a method based on in-situ aminolysis of poly(pentafluorophenyl acrylate) (pPFPA) capable of generating arbitrary hydrophilic surface is proposed, enabling high design freedom and abundant choices of hydrophilic molecules. Simply immersing pPFPA coated substrates into 3-((3-aminopropyl)dimethylammonio)propane-1-sulfonate (ADPS), β-alanine and amine-terminal poly(ethylene glycol) (NH2-PEG) solutions for two hours drastically reduces the water contact angle of the corresponding surfaces, indicating the high efficiency and excellent generality of such method. Systematical studies reveal that these coatings are able to mitigate fog formation, self-clean the oil contaminant and exhibit excellent antifouling performance against algae. Notably, relying on the fast and quantitative feature of the aminolysis, these hydrophilic surfaces possess excellent regeneration capability and well-recover their hydrophilic feature after being physically damaged. This work represents a facile and universal way to fabricate versatile hydrophilic surfaces for multi-functional applications such as self-cleaning, patterning, sensing, antifogging and anti-biofouling.
Surface hydrophilization is required for numbers of applications such as biosensor, biomedical implants and marine coating. However, the preparation of hydrophilic surface from a solid substrate still suffers from limited thicknesses, complex procedures, restricted substrates and harsh conditions. Herein, a method based on in-situ aminolysis of poly(pentafluorophenyl acrylate) (pPFPA) capable of generating arbitrary hydrophilic surface is proposed, enabling high design freedom and abundant choices of hydrophilic molecules. Simply immersing pPFPA coated substrates into 3-((3-aminopropyl)dimethylammonio)propane-1-sulfonate (ADPS), β-alanine and amine-terminal poly(ethylene glycol) (NH2-PEG) solutions for two hours drastically reduces the water contact angle of the corresponding surfaces, indicating the high efficiency and excellent generality of such method. Systematical studies reveal that these coatings are able to mitigate fog formation, self-clean the oil contaminant and exhibit excellent antifouling performance against algae. Notably, relying on the fast and quantitative feature of the aminolysis, these hydrophilic surfaces possess excellent regeneration capability and well-recover their hydrophilic feature after being physically damaged. This work represents a facile and universal way to fabricate versatile hydrophilic surfaces for multi-functional applications such as self-cleaning, patterning, sensing, antifogging and anti-biofouling.
2021, 40(11): 1535-1540
doi: 10.14102/j.cnki.0254-5861.2011-3201
Abstract:
Here we report the utilization of inorganic-organic hybrid (IOH) as a new type of cathode material for aqueous Zn-ion batteries. The IOH possessing a unique lattice-water-rich layered structure achieves high long-term cycling stability (81.5% capacity retention over 1500 cycles) and ultrafast charging capability (~90% state of charge about 1 minute).
Here we report the utilization of inorganic-organic hybrid (IOH) as a new type of cathode material for aqueous Zn-ion batteries. The IOH possessing a unique lattice-water-rich layered structure achieves high long-term cycling stability (81.5% capacity retention over 1500 cycles) and ultrafast charging capability (~90% state of charge about 1 minute).
2021, 40(11): 1541-1549
doi: 10.14102/j.cnki.0254-5861.2011-3167
Abstract:
Polymer dielectric is superior to its inorganic counterparts due to not only the low cost and intrinsic flexibility, but also the readily tunable dielectric constant, surface charge trap density, charge ejection and releasing ability and dipole moment, and all these properties play decisive roles in regulating the characteristic and performances of organic thin film transistors (OTFT). However, systematical studies on the relationship between structure and properties of polymeric dielectrics are rare. To this end, a series of polymeric dielectrics with well-defined linkages (ester or amide bonds) and predesigned pendant groups (alkyl- and aromatic-groups) are synthesized in high yields. Detailed studies show that the polyamide dielectrics exhibit higher dielectric constant, surface charge trapping density, and better charge storage capability than corresponding polyester dielectrics. Further, increasing the π electron delocalization of the pendant groups generally benefits the charge storage property and transistor memory behavior. Theoretical calculation reveals that the hydrogen bonding between the linkage groups and the energy alignment between polymeric dielectric and semiconductor are responsible for the observed performance differences of OTFT with different polymeric dielectrics. These results may shine light on the design of polymeric dielectrics for OTFTs with different applications.
Polymer dielectric is superior to its inorganic counterparts due to not only the low cost and intrinsic flexibility, but also the readily tunable dielectric constant, surface charge trap density, charge ejection and releasing ability and dipole moment, and all these properties play decisive roles in regulating the characteristic and performances of organic thin film transistors (OTFT). However, systematical studies on the relationship between structure and properties of polymeric dielectrics are rare. To this end, a series of polymeric dielectrics with well-defined linkages (ester or amide bonds) and predesigned pendant groups (alkyl- and aromatic-groups) are synthesized in high yields. Detailed studies show that the polyamide dielectrics exhibit higher dielectric constant, surface charge trapping density, and better charge storage capability than corresponding polyester dielectrics. Further, increasing the π electron delocalization of the pendant groups generally benefits the charge storage property and transistor memory behavior. Theoretical calculation reveals that the hydrogen bonding between the linkage groups and the energy alignment between polymeric dielectric and semiconductor are responsible for the observed performance differences of OTFT with different polymeric dielectrics. These results may shine light on the design of polymeric dielectrics for OTFTs with different applications.
