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2020 Volume 39 Issue 3
2020, 39(3): 381-387
doi: 10.14102/j.cnki.0254-5861.2011-2766
Abstract:
Scanning probe microscopy (SPM) stands out as one of the most powerful tools for characterizing the solid surface and the adsorbed molecules with Ångström resolution in real space. In particular, this unique technique provides an unprecedented opportunity for directly probing the low-dimensional ices at surfaces. In this perspective, we first review the recent advances of scanning tunneling microscopy (STM) imaging of various two-dimensional (2D) ice structures on metal[1 -7 ], insulator[8 -12 ], graphite[13 -15 ] surfaces and under strong confinement[10 , 16 -19 ]. We then introduce that noncontact atomic-force microscopy (AFM) with a CO-terminated tip enables atomic imaging of a genuine 2D ice grown on a hydrophobic Au(111) surface with minimal perturbation[20 ], paying particular attention to the growth processes at the edges of 2D ice. In the end, we present an outlook on the future applications of 2D ice as well as the relation between the 2D and 3D ice growth.
Scanning probe microscopy (SPM) stands out as one of the most powerful tools for characterizing the solid surface and the adsorbed molecules with Ångström resolution in real space. In particular, this unique technique provides an unprecedented opportunity for directly probing the low-dimensional ices at surfaces. In this perspective, we first review the recent advances of scanning tunneling microscopy (STM) imaging of various two-dimensional (2D) ice structures on metal[
2020, 39(3): 388-394
doi: 10.14102/j.cnki.0254-5861.2011-2765
Abstract:
As a key material for the development of mild aqueous rechargeable Zn/MnO2 cells, MnO2 has attracted much attention. This article presents some issues of MnO2, provides some strategies improving battery performance of MnO2 electrode, as well as makes a perspective on future research and development of MnO2 materials. This article offers a profound insight on structure/property relationship of MnO2, and benefits a lot to those involved in energy storage and conversion applications.
As a key material for the development of mild aqueous rechargeable Zn/MnO2 cells, MnO2 has attracted much attention. This article presents some issues of MnO2, provides some strategies improving battery performance of MnO2 electrode, as well as makes a perspective on future research and development of MnO2 materials. This article offers a profound insight on structure/property relationship of MnO2, and benefits a lot to those involved in energy storage and conversion applications.
2020, 39(3): 395-400
doi: 10.14102/j.cnki.0254-5861.2011-2779
Abstract:
Nowadays, researches on developing new etching materials to optimize the Ag/Si contact interface in silicon solar cells (SSCs) are rare, which alleviates the further development of SSCs. In this study, silver tellurite (Ag2TeO3, monoclinic, P21/a(14)) is synthesized and developed as an excellent etching material in SSCs. The Ag2TeO3 displays a low starting temperature of etching Si3N4 of ~545 ℃, which is ~160 ℃ lower than that of PbO. Besides, by applying Ag2TeO3, conductive silver nanoparticles with a length of about 300~500 nm and a thickness of ~50 nm form in the Ag/Si contact interface, which effectively reduces the Ag-Si contact resistance, and leads to a high solar cell efficiency of ~18.4%. This study opens a new window for further enhancing the solar cell efficiency in the future.
Nowadays, researches on developing new etching materials to optimize the Ag/Si contact interface in silicon solar cells (SSCs) are rare, which alleviates the further development of SSCs. In this study, silver tellurite (Ag2TeO3, monoclinic, P21/a(14)) is synthesized and developed as an excellent etching material in SSCs. The Ag2TeO3 displays a low starting temperature of etching Si3N4 of ~545 ℃, which is ~160 ℃ lower than that of PbO. Besides, by applying Ag2TeO3, conductive silver nanoparticles with a length of about 300~500 nm and a thickness of ~50 nm form in the Ag/Si contact interface, which effectively reduces the Ag-Si contact resistance, and leads to a high solar cell efficiency of ~18.4%. This study opens a new window for further enhancing the solar cell efficiency in the future.
2020, 39(3): 401-414
doi: 10.14102/j.cnki.0254-5861.2011-2787
Abstract:
Two-dimensional (2D) materials attracted substantial attention due to their extraordinary physical properties resulting from the unique atomic thickness. 2D materials could be considered as material systems with flat surfaces at both sides, while the van der Waals gap is a natural out-of-plane interface between two monolayers. However, defects are inevitably presented and often cause significant surface and interface reconstruction, which modify the physical properties of the materials being investigated. In this review article, we reviewed the effort achieved in probing the defect structures and the reconstruction of surface and interface in novel 2D materials through aberration corrected low voltage scanning transmission electron microscopy (LVSTEM). The LVSTEM technique enables us to unveil the intrinsic atomic structure of defects atom-by-atom, and even directly visualize the dynamical reconstruction process with single atom precision. The effort in understanding the defect structures and their contributions in the surface and interface reconstructions in 2D materials shed light on the origin of their novel physical phenomenon, and also pave the way for defect engineering in future potential applications.
Two-dimensional (2D) materials attracted substantial attention due to their extraordinary physical properties resulting from the unique atomic thickness. 2D materials could be considered as material systems with flat surfaces at both sides, while the van der Waals gap is a natural out-of-plane interface between two monolayers. However, defects are inevitably presented and often cause significant surface and interface reconstruction, which modify the physical properties of the materials being investigated. In this review article, we reviewed the effort achieved in probing the defect structures and the reconstruction of surface and interface in novel 2D materials through aberration corrected low voltage scanning transmission electron microscopy (LVSTEM). The LVSTEM technique enables us to unveil the intrinsic atomic structure of defects atom-by-atom, and even directly visualize the dynamical reconstruction process with single atom precision. The effort in understanding the defect structures and their contributions in the surface and interface reconstructions in 2D materials shed light on the origin of their novel physical phenomenon, and also pave the way for defect engineering in future potential applications.
2020, 39(3): 415-420
doi: 10.14102/j.cnki.0254-5861.2011-2463
Abstract:
Performance of carbon nanotube (CNT) and their attached metal oxides (manganese oxide (MnO) and cadmium dioxide (CdO2)) structures as anode electrodes in lithium-ion battery (LIB) and potassium-ion battery (KIB) are investigated. The Gibbs free energy of adsorption of Li and K atoms/ions on surfaces of CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO2 are calculated. The cell voltages (Vcell) of Li and K atoms/ions adsorption on studied surfaces are examined. The Vcell of LIBs with metal-oxides attached to CNT (8, 0) as anode electrodes are higher than those KIBs. The adsorbed metal oxides (MnO and CdO2) on CNT (8, 0) increased the charges, electronic conductivity and Vcell of LIB and KIB, efficiently. The CNT (8, 0)-CdO2 as anode electrodes in LIB and KIB is proposed.
Performance of carbon nanotube (CNT) and their attached metal oxides (manganese oxide (MnO) and cadmium dioxide (CdO2)) structures as anode electrodes in lithium-ion battery (LIB) and potassium-ion battery (KIB) are investigated. The Gibbs free energy of adsorption of Li and K atoms/ions on surfaces of CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO2 are calculated. The cell voltages (Vcell) of Li and K atoms/ions adsorption on studied surfaces are examined. The Vcell of LIBs with metal-oxides attached to CNT (8, 0) as anode electrodes are higher than those KIBs. The adsorbed metal oxides (MnO and CdO2) on CNT (8, 0) increased the charges, electronic conductivity and Vcell of LIB and KIB, efficiently. The CNT (8, 0)-CdO2 as anode electrodes in LIB and KIB is proposed.
3D-QSAR Analysis of Naphthyltriazole (Lesinurad) Analogs as Potent Inhibitors of Urate Transporter 1
2020, 39(3): 421-436
doi: 10.14102/j.cnki.0254-5861.2011-2469
Abstract:
To obtain useful information for identifying inhibitors of urate transporter 1 (URAT1), three-dimensional quantitative structure-activity relationship (3D-QSAR) analysis was conducted for a series of lesinurad analogs via Topomer comparative molecular field analysis (CoMFA). A 3D-QSAR model was established using a training set of 51 compounds and externally validated with a test set of 17 compounds. The Topomer CoMFA model obtained (q2 = 0.976, r2 = 0.990) was robust and satisfactory. Subsequently, seven compounds with significant URAT1 inhibitory activity were designed according to the contour maps produced by the Topomer CoMFA model.
To obtain useful information for identifying inhibitors of urate transporter 1 (URAT1), three-dimensional quantitative structure-activity relationship (3D-QSAR) analysis was conducted for a series of lesinurad analogs via Topomer comparative molecular field analysis (CoMFA). A 3D-QSAR model was established using a training set of 51 compounds and externally validated with a test set of 17 compounds. The Topomer CoMFA model obtained (q2 = 0.976, r2 = 0.990) was robust and satisfactory. Subsequently, seven compounds with significant URAT1 inhibitory activity were designed according to the contour maps produced by the Topomer CoMFA model.
2020, 39(3): 437-442
doi: 10.14102/j.cnki.0254-5861.2011-2474
Abstract:
Two ternary Eu-Hf-Q (Q = S, Se) chalcogenides, EuHfSe3 (1) and Eu5Hf3S12 (2), have been synthesized by a facile solid state routine and structurally characterized by single-crystal X-ray diffraction technique. They crystallize in the orthorhombic space group Pnma (1) or hexagonal P62m (2), and diverse Hf-Q chains exist in their 3D structures. The electronic structure of 1 is also calculated according to density functional theory.
Two ternary Eu-Hf-Q (Q = S, Se) chalcogenides, EuHfSe3 (1) and Eu5Hf3S12 (2), have been synthesized by a facile solid state routine and structurally characterized by single-crystal X-ray diffraction technique. They crystallize in the orthorhombic space group Pnma (1) or hexagonal P62m (2), and diverse Hf-Q chains exist in their 3D structures. The electronic structure of 1 is also calculated according to density functional theory.
2020, 39(3): 443-451
doi: 10.14102/j.cnki.0254-5861.2011-2499
Abstract:
Hydrogen is known to play a negative role in mechanical properties of steel due to hydrogen embrittlement. Surface strain modifies the surface reactivity. In this paper, we employed spin-polarized periodic density functional to study the atomic H adsorption and diffusion on the biaxial strained Fe(110) surface. The result shows that the adsorption of H at the Tf site is the most stable on compressive surface and tensile surface. And H atom on the top site relaxes to Tf site on the strained surface. The adsorbed hydrogen atom at all calculated adsorption sites relaxes towards the surface due to the tensile strain. Lattice compression makes the bonding strength weaker between H atom and the surface. The analysis of the partial density of states shows that H 1s orbital hybridizes with the Fe 4s orbital. The result of charge density difference shows electrons are transferred from Fe to H atom. Compressive strain reduces the transferred electrons and decreases the Mulliken electrons of Fe 4s orbital, which weaken the bonding interaction between H and Fe atoms. H atom diffuses into subsurface through a distorted tetrahedron. Surface strain does not change diffusion path but affects the diffusion barrier energy. Tetrahedron gap volume in the transition state of compressive system decreases to increase the diffusion barrier. This suggests compressive strain impedes H penetrating into the Fe subsurface. The present results indicate that it is a way to control adsorption and diffusion of hydrogen on the Fe surface by surface strain.
Hydrogen is known to play a negative role in mechanical properties of steel due to hydrogen embrittlement. Surface strain modifies the surface reactivity. In this paper, we employed spin-polarized periodic density functional to study the atomic H adsorption and diffusion on the biaxial strained Fe(110) surface. The result shows that the adsorption of H at the Tf site is the most stable on compressive surface and tensile surface. And H atom on the top site relaxes to Tf site on the strained surface. The adsorbed hydrogen atom at all calculated adsorption sites relaxes towards the surface due to the tensile strain. Lattice compression makes the bonding strength weaker between H atom and the surface. The analysis of the partial density of states shows that H 1s orbital hybridizes with the Fe 4s orbital. The result of charge density difference shows electrons are transferred from Fe to H atom. Compressive strain reduces the transferred electrons and decreases the Mulliken electrons of Fe 4s orbital, which weaken the bonding interaction between H and Fe atoms. H atom diffuses into subsurface through a distorted tetrahedron. Surface strain does not change diffusion path but affects the diffusion barrier energy. Tetrahedron gap volume in the transition state of compressive system decreases to increase the diffusion barrier. This suggests compressive strain impedes H penetrating into the Fe subsurface. The present results indicate that it is a way to control adsorption and diffusion of hydrogen on the Fe surface by surface strain.
2020, 39(3): 452-458
doi: 10.14102/j.cnki.0254-5861.2011-2459
Abstract:
The title compound 2-chloro-N-(o-tolylcarbamoyl)nicotinamide (C14H12ClN3O2) was synthesized, and its structure was confirmed by 1H NMR, H RMS and X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 7.8356(7), b = 12.7949(8), c = 13.6326(10) Å, β = 91.929(7)°, V = 1365.97(18) Å3, Z = 4, the final R = 0.0416 and wR = 0.0971 for 2467 observed reflections with I > 2σ(I). The preliminary biological test shows that the title compound has certain fungicidal activities.
The title compound 2-chloro-N-(o-tolylcarbamoyl)nicotinamide (C14H12ClN3O2) was synthesized, and its structure was confirmed by 1H NMR, H RMS and X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 7.8356(7), b = 12.7949(8), c = 13.6326(10) Å, β = 91.929(7)°, V = 1365.97(18) Å3, Z = 4, the final R = 0.0416 and wR = 0.0971 for 2467 observed reflections with I > 2σ(I). The preliminary biological test shows that the title compound has certain fungicidal activities.
2020, 39(3): 459-466
doi: 10.14102/j.cnki.0254–5861.2011–2465
Abstract:
Tri(o-bromobenzyl)tin diethyldithiocarbamate (1) and tri(m-fluorobenzyl)tin pyrrolidine dithiocarbamate (2) have been synthesized and characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C and 119Sn), thermogravimetric analysis and single-crystal X-ray diffraction. The two complexes crystallize in the triclinic system space group P\begin{document}$ \overline 1 $\end{document}
Tri(o-bromobenzyl)tin diethyldithiocarbamate (1) and tri(m-fluorobenzyl)tin pyrrolidine dithiocarbamate (2) have been synthesized and characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C and 119Sn), thermogravimetric analysis and single-crystal X-ray diffraction. The two complexes crystallize in the triclinic system space group P
2020, 39(3): 467-484
doi: 10.14102/j.cnki.0254-5861.2011-2506
Abstract:
Three new halogenated pyridyl hydrazones, namely 4-chlorobenzaldehyde-4-chlo-ropyridine-2-formyl acylhydrazone (C13H9Cl2N3O, 3a), 4-bromobenzaldehyde-4-chloropyridine-2-formyl acylhydrazone (C13H9BrClN3O, 3b) and 4-iodobenzaldehyde-4-chloropyridine-2-formyl acylhydrazone (C13H9ClIN3O, 3c), have been synthesized and characterized by elemental analysis, IR, 1H NMR, and single-crystal X-ray diffraction. The X-ray diffraction analysis revealed that 3a~3c crystallize in monoclinic with space group Cc. The units of 3a~3c were linked by intermolecular N–H···X (X = Cl, Br, I) hydrogen bonds into 2D layered structures, which were further extended into 3D networks by a series of π-π stacking interactions. Thermogravimetric analysis showed that all of them possessed higher thermal stabilities. The reactivities toward calf thymus DNA (ct-DNA) and bovine serum albumin (BSA) of 3a~3c were investigated by UV-vis and fluorescent spectroscopy as well as molecular docking simulation. Both theoretical and experimental results indicated that 3a~3c bound to ct-DNA in the mode of minor groove binding, and interacted with BSA through the hydrophobic cavity near TRP213. Besides, the orders of binding affinities of 3a~3c to ct-DNA and BSA were both 3c > 3b > 3a, which were the same as that of antibacterial activities. Thus, the interactions of iodinated acylhydrazone with biological targets were stronger than that of chlorinated and brominated acylhydrazones, which provided a representative case for halogenation of lead compounds in rational drug design.
Three new halogenated pyridyl hydrazones, namely 4-chlorobenzaldehyde-4-chlo-ropyridine-2-formyl acylhydrazone (C13H9Cl2N3O, 3a), 4-bromobenzaldehyde-4-chloropyridine-2-formyl acylhydrazone (C13H9BrClN3O, 3b) and 4-iodobenzaldehyde-4-chloropyridine-2-formyl acylhydrazone (C13H9ClIN3O, 3c), have been synthesized and characterized by elemental analysis, IR, 1H NMR, and single-crystal X-ray diffraction. The X-ray diffraction analysis revealed that 3a~3c crystallize in monoclinic with space group Cc. The units of 3a~3c were linked by intermolecular N–H···X (X = Cl, Br, I) hydrogen bonds into 2D layered structures, which were further extended into 3D networks by a series of π-π stacking interactions. Thermogravimetric analysis showed that all of them possessed higher thermal stabilities. The reactivities toward calf thymus DNA (ct-DNA) and bovine serum albumin (BSA) of 3a~3c were investigated by UV-vis and fluorescent spectroscopy as well as molecular docking simulation. Both theoretical and experimental results indicated that 3a~3c bound to ct-DNA in the mode of minor groove binding, and interacted with BSA through the hydrophobic cavity near TRP213. Besides, the orders of binding affinities of 3a~3c to ct-DNA and BSA were both 3c > 3b > 3a, which were the same as that of antibacterial activities. Thus, the interactions of iodinated acylhydrazone with biological targets were stronger than that of chlorinated and brominated acylhydrazones, which provided a representative case for halogenation of lead compounds in rational drug design.
2020, 39(3): 485-492
doi: 10.14102/j.cnki.0254-5861.2011-2447
Abstract:
Compared with borates, carbonates, nitrates and phosphates, sulfates have been ignored as nonlinear optical (NLO) materials for a long time. Recently, researchers started to realize sulfates which have the potential as NLO materials, and synthesized some sulfate NLO materials by the water solution method and solvothermal method. However, all these sulfate NLO materials have the same problem of low thermal stability. Here, we synthesized a new Cs4Mg6(SO4)8, which crystallizes in the orthorhombic space group P212121 with a = 9.102, b = 9.955, c = 16.127 Å, V = 1461.3 Å3, Z = 2, F(000) = 1352, μ = 5.777 mm-1, R = 0.0213 and wR = 0.0480. The single crystal structure can be described as a three-dimensional framework constructed by MgO6 octahedra and SO4 tetrahedra. Relevant optical measurements indicate that Cs4Mg6(SO4)8 is short-wave ultraviolet transparent and has a moderate second harmonic generation response. Theoretical calculations by the CASTEP package reveal that S–O groups are NLO-active anionic groups. Significantly, Cs4Mg6(SO4)8 has high thermal stability up to 781 ℃ based on thermal analyses. We believe that our work will provide a new strategy for researchers to develop new sulfate short-wave ultraviolet NLO materials of high thermal stability.
Compared with borates, carbonates, nitrates and phosphates, sulfates have been ignored as nonlinear optical (NLO) materials for a long time. Recently, researchers started to realize sulfates which have the potential as NLO materials, and synthesized some sulfate NLO materials by the water solution method and solvothermal method. However, all these sulfate NLO materials have the same problem of low thermal stability. Here, we synthesized a new Cs4Mg6(SO4)8, which crystallizes in the orthorhombic space group P212121 with a = 9.102, b = 9.955, c = 16.127 Å, V = 1461.3 Å3, Z = 2, F(000) = 1352, μ = 5.777 mm-1, R = 0.0213 and wR = 0.0480. The single crystal structure can be described as a three-dimensional framework constructed by MgO6 octahedra and SO4 tetrahedra. Relevant optical measurements indicate that Cs4Mg6(SO4)8 is short-wave ultraviolet transparent and has a moderate second harmonic generation response. Theoretical calculations by the CASTEP package reveal that S–O groups are NLO-active anionic groups. Significantly, Cs4Mg6(SO4)8 has high thermal stability up to 781 ℃ based on thermal analyses. We believe that our work will provide a new strategy for researchers to develop new sulfate short-wave ultraviolet NLO materials of high thermal stability.
2020, 39(3): 493-499
doi: 10.14102/j.cnki.0254-5861.2011-2457
Abstract:
Tungsten disulfide (WS2) has been recognized as a promising anode material for rechargeable potassium-ion batteries (PIBs). However, its K-ion intercalation capacity is limited to ~60 mAh·g-1. Here, we report a WS2-graphene composite anode which is fabricated through simple filtration of liquid-phase exfoliated WS2 and graphene nanosheet delivers a significantly improved specific capacity of 137 mAh·g-1 at a current density of 10 mA·g-1. The composite anodes also exhibit remarkable rate capability and long-term cyclability over 500 cycles. These results highlight the WS2-graphene composite structure as a promising anode material for long lifespan rechargeable potassium-ion batteries.
Tungsten disulfide (WS2) has been recognized as a promising anode material for rechargeable potassium-ion batteries (PIBs). However, its K-ion intercalation capacity is limited to ~60 mAh·g-1. Here, we report a WS2-graphene composite anode which is fabricated through simple filtration of liquid-phase exfoliated WS2 and graphene nanosheet delivers a significantly improved specific capacity of 137 mAh·g-1 at a current density of 10 mA·g-1. The composite anodes also exhibit remarkable rate capability and long-term cyclability over 500 cycles. These results highlight the WS2-graphene composite structure as a promising anode material for long lifespan rechargeable potassium-ion batteries.
2020, 39(3): 500-510
doi: 10.14102/j.cnki.0254–5861.2011–2569
Abstract:
A new kind of co-crystal of buprofezin (C16H24FN3OS) with hydrofluoric acid has been prepared through evaporation technique. It crystallizes in the triclinic space group P\begin{document}$ \overline 1 $\end{document}
A new kind of co-crystal of buprofezin (C16H24FN3OS) with hydrofluoric acid has been prepared through evaporation technique. It crystallizes in the triclinic space group P
2020, 39(3): 511-518
doi: 10.14102/j.cnki.0254-5861.2011-2452
Abstract:
A series of Bi3+-doped YAG: Ce3+, Mn2+ ceramics was synthesized successfully by gel-casting method and structurally characterized by XRD and SEM. The doping effect and related mechanism of Bi3+ upon the luminescent property were studied. It can be assigned to the energy transfer of multipolar interaction from Bi3+ to Ce3+, leading to the improvement of emission intensity about 58% for 0.0001 Bi3+ and 0.05 Mn2+ doping. In addition, the emission is significantly red-shifted with the peak at 590 nm for the Y2.9939Ce0.006Bi0.0001Al4.96Mn0.02Si0.02O12 ceramic specimen with in-line transmittance 81.6% at 1100 nm. The LED module assembled from Y2.9939Ce0.006Bi0.0001Al4.96Mn0.02Si0.02O12 ceramic owns correlated color temperature (CCT) of 3960 K and luminous efficiency (LE) of 92 lm/W, implying that doping Bi3+ shows a good sensitization effect in the YAG: Ce3+, Mn2+ ceramic system and further serving as an attracting phosphor candidates for warm WLEDs applications.
A series of Bi3+-doped YAG: Ce3+, Mn2+ ceramics was synthesized successfully by gel-casting method and structurally characterized by XRD and SEM. The doping effect and related mechanism of Bi3+ upon the luminescent property were studied. It can be assigned to the energy transfer of multipolar interaction from Bi3+ to Ce3+, leading to the improvement of emission intensity about 58% for 0.0001 Bi3+ and 0.05 Mn2+ doping. In addition, the emission is significantly red-shifted with the peak at 590 nm for the Y2.9939Ce0.006Bi0.0001Al4.96Mn0.02Si0.02O12 ceramic specimen with in-line transmittance 81.6% at 1100 nm. The LED module assembled from Y2.9939Ce0.006Bi0.0001Al4.96Mn0.02Si0.02O12 ceramic owns correlated color temperature (CCT) of 3960 K and luminous efficiency (LE) of 92 lm/W, implying that doping Bi3+ shows a good sensitization effect in the YAG: Ce3+, Mn2+ ceramic system and further serving as an attracting phosphor candidates for warm WLEDs applications.
A New Pillared-layer Framework with CoⅡ 4-Triazole Magnetic Layer Exhibiting Strong Spin-frustration
2020, 39(3): 519-525
doi: 10.14102/j.cnki.0254-5861.2011-2423
Abstract:
One new coordination polymer, [Co4(H2O)4(μ3-OH)2(atz)2(L)]n (1), was solvothermally prepared by the reaction of 3-amino-1, 2, 4-triazole (Hatz), 4, 8-disulfonyl-2, 6-naphthalenedicarboxylic acid (H4L) and CoⅡ salt. It crystallizes in monoclinic system, space group P21/c with a = 10.4454(7), b = 12.2214(8), c = 10.0818(7) Å, β = 102.284(7), V = 1257.56(15) Å3, Dc = 2.325 g/cm3, Mr = 880.24, Z = 2, F(000) = 880, μ = 2.859 mm-1, the final R = 0.0426 and wR = 0.0822 for 5526 observed reflections with I > 2σ(I). Structural analyses indicate that 1 exhibits a three-dimensional (3D) pillared-layer framework with triazolate extended Co4Ⅱ layers supported by rigid L4- connectors. Magnetically, complex 1 displays strong spin-frustrated antiferromagnetism due to the triangular magnetic lattice and cooperative antiferromagnetic couplings mediated by quadruple heterobridges.
One new coordination polymer, [Co4(H2O)4(μ3-OH)2(atz)2(L)]n (1), was solvothermally prepared by the reaction of 3-amino-1, 2, 4-triazole (Hatz), 4, 8-disulfonyl-2, 6-naphthalenedicarboxylic acid (H4L) and CoⅡ salt. It crystallizes in monoclinic system, space group P21/c with a = 10.4454(7), b = 12.2214(8), c = 10.0818(7) Å, β = 102.284(7), V = 1257.56(15) Å3, Dc = 2.325 g/cm3, Mr = 880.24, Z = 2, F(000) = 880, μ = 2.859 mm-1, the final R = 0.0426 and wR = 0.0822 for 5526 observed reflections with I > 2σ(I). Structural analyses indicate that 1 exhibits a three-dimensional (3D) pillared-layer framework with triazolate extended Co4Ⅱ layers supported by rigid L4- connectors. Magnetically, complex 1 displays strong spin-frustrated antiferromagnetism due to the triangular magnetic lattice and cooperative antiferromagnetic couplings mediated by quadruple heterobridges.
2020, 39(3): 526-534
doi: 10.14102/j.cnki.0254–5861.2011–2427
Abstract:
This work presents a highly active and reusable heterogeneous film catalytic assembly for hydrogenation reduction of aromatic nitro compounds. The multilayer structures of PEI-(K2PdCl4-P1)n-film (PEI = polyethylenmine, P1 = 3-amino-3-(4-pyridinyl)-propionitrile) bound to quartz slides were fabricated by layer-by-layer (LbL) self-assembly method. Various characterization techniques including X-ray photoelectron spectroscopy (XPS), inductively coupled plasma OES spectrometer (ICP), UV-vis spectroscopy and atomic force microscopy (AFM) were employed to reveal the growth process of the resulting LbL multilayers in detail. Subsequent in situ reduction by H2 produced Pd nanoparticles embedded in such films were used as catalyst for the hydrogenation of nitroarenes. The catalytic performance test shows that the thin film catalyst can be applied to the hydrogenation reaction of various substituted nitroaromatics, and exhibits good catalytic activity and good catalyst stability. It is worth mentioning that our catalytic films can be easily removed from the reaction system in any time during the reaction, and the catalytic activity could be fully recovered when reused directly in another catalytic cycle for five times.
This work presents a highly active and reusable heterogeneous film catalytic assembly for hydrogenation reduction of aromatic nitro compounds. The multilayer structures of PEI-(K2PdCl4-P1)n-film (PEI = polyethylenmine, P1 = 3-amino-3-(4-pyridinyl)-propionitrile) bound to quartz slides were fabricated by layer-by-layer (LbL) self-assembly method. Various characterization techniques including X-ray photoelectron spectroscopy (XPS), inductively coupled plasma OES spectrometer (ICP), UV-vis spectroscopy and atomic force microscopy (AFM) were employed to reveal the growth process of the resulting LbL multilayers in detail. Subsequent in situ reduction by H2 produced Pd nanoparticles embedded in such films were used as catalyst for the hydrogenation of nitroarenes. The catalytic performance test shows that the thin film catalyst can be applied to the hydrogenation reaction of various substituted nitroaromatics, and exhibits good catalytic activity and good catalyst stability. It is worth mentioning that our catalytic films can be easily removed from the reaction system in any time during the reaction, and the catalytic activity could be fully recovered when reused directly in another catalytic cycle for five times.
2020, 39(3): 535-542
doi: 10.14102/j.cnki.0254-5861.2011-2440
Abstract:
A new supramolecular self-assembly [Li(H2O)2]2[(H2O@Me10CB[5])][PtCl6]·7H2O (1, Me10CB[5] = decamethylcucurbit[5]uril), has been successfully constructed with Me10CB[5] and [PtCl6]2- anion in the presence of lithium cation (Li+). Single-crystal X-ray diffraction study reveals that compound 1 crystallizes in monoclinic space group P21/n with a = 11.1681(18), b = 28.5425(4), c = 18.9342(3) Å, β = 99.0143(15)°, V = 5961.02(16) Å3, Z = 4, F(000) = 3224, μ = 2.714 mm-1, R = 0.0470 and wR = 0.1076 (I > 2σ(I)). In the supramolecular self-assembly, two of the portal carbonyl oxygen atoms of Me10CB[5] are coordinated to Li+ cation, yielding a "half-open" molecular capsule. Then adjacent molecular capsules are connected with each other through hydrogen-bonding to form a one-dimensional (1D) supramolecular chain structure. The [PtCl6]2- anions are fixed on one side of the 1D supramolecular chain through supramolecular interactions. The thermal stability, electronic valence and morphology of compound 1 are also investigated.
A new supramolecular self-assembly [Li(H2O)2]2[(H2O@Me10CB[5])][PtCl6]·7H2O (1, Me10CB[5] = decamethylcucurbit[5]uril), has been successfully constructed with Me10CB[5] and [PtCl6]2- anion in the presence of lithium cation (Li+). Single-crystal X-ray diffraction study reveals that compound 1 crystallizes in monoclinic space group P21/n with a = 11.1681(18), b = 28.5425(4), c = 18.9342(3) Å, β = 99.0143(15)°, V = 5961.02(16) Å3, Z = 4, F(000) = 3224, μ = 2.714 mm-1, R = 0.0470 and wR = 0.1076 (I > 2σ(I)). In the supramolecular self-assembly, two of the portal carbonyl oxygen atoms of Me10CB[5] are coordinated to Li+ cation, yielding a "half-open" molecular capsule. Then adjacent molecular capsules are connected with each other through hydrogen-bonding to form a one-dimensional (1D) supramolecular chain structure. The [PtCl6]2- anions are fixed on one side of the 1D supramolecular chain through supramolecular interactions. The thermal stability, electronic valence and morphology of compound 1 are also investigated.
2020, 39(3): 543-550
doi: 10.14102/j.cnki.0254–5861.2011–2456
Abstract:
Basic magnesium carbonate (4MgCO3·Mg(OH)2·4H2O) with spherical-like structure was synthesized through precursors thermal decomposition. The precursor of magnesium carbonate trihydrates (MgCO3·3H2O) was synthesized by brine and ammonium bicarbonate, and the thermal decomposition conditions were investigated in detail. The obtained particulate was characterized using SEM, XRD and laser particle analyzer. The result showed that it was easy to obtain spherical-like 4MgCO3·Mg(OH)2·4H2O by precursor thermal decomposition at 80~100 ℃ with thermal decomposition time 90 min, stirring time 15 min and the liquid initial concentration 0.1 mol/L, while rod-like 4MgCO3·Mg(OH)2·4H2O with a surface of "house of card" structure was more likely to be obtained at low temperature (55 ℃), and rosette-like products were obtained at a little higher temperature (80 ℃) by direct synthesis.
Basic magnesium carbonate (4MgCO3·Mg(OH)2·4H2O) with spherical-like structure was synthesized through precursors thermal decomposition. The precursor of magnesium carbonate trihydrates (MgCO3·3H2O) was synthesized by brine and ammonium bicarbonate, and the thermal decomposition conditions were investigated in detail. The obtained particulate was characterized using SEM, XRD and laser particle analyzer. The result showed that it was easy to obtain spherical-like 4MgCO3·Mg(OH)2·4H2O by precursor thermal decomposition at 80~100 ℃ with thermal decomposition time 90 min, stirring time 15 min and the liquid initial concentration 0.1 mol/L, while rod-like 4MgCO3·Mg(OH)2·4H2O with a surface of "house of card" structure was more likely to be obtained at low temperature (55 ℃), and rosette-like products were obtained at a little higher temperature (80 ℃) by direct synthesis.
2020, 39(3): 551-558
doi: 10.14102/j.cnki.0254–5861.2011–2475
Abstract:
A novel zinc complex [ZnL(bipy)(H2O)]⋅H2O with mixed ligands of 3-hydroxy-2-methylquinoline-4-carboxylic acid (HL) and bipy (bipy = 2, 2΄-bipyridine) was synthesized by solvothermal reaction and its crystal structure was determined by single-crystal X-ray diffraction technique. The title compound crystallizes in the orthorhombic system of Pbca space group, and exists as an isolated mononuclear complex. The intermolecular hydrogen bonds and strong π…π stacking interactions form a three-dimensional (3-D) supramolecular network. Solid-state photoluminescence spectrum reveals that it shows an emission in the blue region of the light spectrum. Time-dependent density functional theory (TDDFT) calculations reveal that this emission can be attributed to ligand-to-ligand charge transfer (LLCT). Solid-state diffuse reflectance data show that there is a narrow optical band gap of 1.83 eV.
A novel zinc complex [ZnL(bipy)(H2O)]⋅H2O with mixed ligands of 3-hydroxy-2-methylquinoline-4-carboxylic acid (HL) and bipy (bipy = 2, 2΄-bipyridine) was synthesized by solvothermal reaction and its crystal structure was determined by single-crystal X-ray diffraction technique. The title compound crystallizes in the orthorhombic system of Pbca space group, and exists as an isolated mononuclear complex. The intermolecular hydrogen bonds and strong π…π stacking interactions form a three-dimensional (3-D) supramolecular network. Solid-state photoluminescence spectrum reveals that it shows an emission in the blue region of the light spectrum. Time-dependent density functional theory (TDDFT) calculations reveal that this emission can be attributed to ligand-to-ligand charge transfer (LLCT). Solid-state diffuse reflectance data show that there is a narrow optical band gap of 1.83 eV.
2020, 39(3): 559-566
doi: 10.14102/j.cnki.0254-5861.2011-2586
Abstract:
A new terbium(Ⅲ) metal-organic framework [Tb(HL)(H2O)] (TbL) based on a new synthetic ligand 9-(2, 6-dicarboxy-pyridin-4-yl)-9H-carbazole-3, 6-dicarboxylic acid (H4L) has been synthesized under solvothermal conditions. Its structure was determined by single-crystal X-ray diffraction analysis, and further characterized by powder X-ray diffraction analysis and IR spectra. The title complex crystallizes in trigonal space group P3212 with a = b = 13.6491(11), c = 32.345(3) Å, γ = 120°, V = 5218.5(10) Å3, C42H20N4O17Tb2, Mr = 1170.46, Dc = 1.117 g/cm3, μ(MoKα) = 2.065 mm-1, F(000) = 1698, GOF = 1.054, Z = 3, the final R = 0.0384 and wR = 0.0771 for 5223 observed reflections (I > 2σ(I)). In TbL, the tri-bridged binuclear Tb2 units are bibridged by two carbazole-3, 6-dicarboxylate moieties to lead to the homochiral parallel arranged helical chains, which are further connected by 2, 6-pyridinedicarboxylate moieties to produce the chiral neutral 3D framework. There are there kinds of 1D channels in the framework with the channel space occupying 53.3% of the total volume. TbL exhibits intense characteristic green emission of Tb3+ ions.
A new terbium(Ⅲ) metal-organic framework [Tb(HL)(H2O)] (TbL) based on a new synthetic ligand 9-(2, 6-dicarboxy-pyridin-4-yl)-9H-carbazole-3, 6-dicarboxylic acid (H4L) has been synthesized under solvothermal conditions. Its structure was determined by single-crystal X-ray diffraction analysis, and further characterized by powder X-ray diffraction analysis and IR spectra. The title complex crystallizes in trigonal space group P3212 with a = b = 13.6491(11), c = 32.345(3) Å, γ = 120°, V = 5218.5(10) Å3, C42H20N4O17Tb2, Mr = 1170.46, Dc = 1.117 g/cm3, μ(MoKα) = 2.065 mm-1, F(000) = 1698, GOF = 1.054, Z = 3, the final R = 0.0384 and wR = 0.0771 for 5223 observed reflections (I > 2σ(I)). In TbL, the tri-bridged binuclear Tb2 units are bibridged by two carbazole-3, 6-dicarboxylate moieties to lead to the homochiral parallel arranged helical chains, which are further connected by 2, 6-pyridinedicarboxylate moieties to produce the chiral neutral 3D framework. There are there kinds of 1D channels in the framework with the channel space occupying 53.3% of the total volume. TbL exhibits intense characteristic green emission of Tb3+ ions.
2020, 39(3): 567-578
doi: 10.14102/j.cnki.0254-5861.2011-2515
Abstract:
A pair of enatiomerically pure ligands, (R-)/(S-)2-(4-carboxyphenyl)-4, 5-dihydrothiazole-4-carboxylic acid (H2LR & H2LS), have been synthesized by the reactions of 4-cyanobenzoic acid with L- and D-cysteine, respectively. Four coordination polymers have been prepared from the ligands and structurally determined by single-crystal X-ray diffraction analysis. Complexes 1R and 1S ([NiL(Py)(H2O)]⋅H2O, for 1R, L = (LR)2-; for 1S, L = (LS)2-) exhibit chiral helical one-dimensional chains, and complexes 2R and 2S ({[ZnL2(H2O)3]⋅CH3CN}n, for 2R L = (LR)2-, for 2S L = (LS)2-) are two-dimensional sheets. Luminescent and chir-optical properties have been investigated and compared with the free ligands. The complexes have blue-shift in luminescence spectrum compared with the free ligands.
A pair of enatiomerically pure ligands, (R-)/(S-)2-(4-carboxyphenyl)-4, 5-dihydrothiazole-4-carboxylic acid (H2LR & H2LS), have been synthesized by the reactions of 4-cyanobenzoic acid with L- and D-cysteine, respectively. Four coordination polymers have been prepared from the ligands and structurally determined by single-crystal X-ray diffraction analysis. Complexes 1R and 1S ([NiL(Py)(H2O)]⋅H2O, for 1R, L = (LR)2-; for 1S, L = (LS)2-) exhibit chiral helical one-dimensional chains, and complexes 2R and 2S ({[ZnL2(H2O)3]⋅CH3CN}n, for 2R L = (LR)2-, for 2S L = (LS)2-) are two-dimensional sheets. Luminescent and chir-optical properties have been investigated and compared with the free ligands. The complexes have blue-shift in luminescence spectrum compared with the free ligands.
2020, 39(3): 579-587
doi: 10.14102/j.cnki.0254-5861.2011-2472
Abstract:
Three title compounds (3~5) have been successfully synthesized via interactive reactions between ferrocenecarboxylic and dehydroabietic acids, which can be characterized by FT-IR, elemental analysis, ESI-MS, and NMR spectroscopy. The crystal structures of compounds 4 and 5 can be determined by single-crystal X-ray diffraction. Compound 4 is of orthorhombic system, space group P212121 with a = 7.7010(5), b = 11.7542(9), c = 28.3173(18) Å, Z = 4, V = 2563.3(3) Å3, Mr = 512.45, Dc = 1.328 g/cm-1, S = 1.041, μ = 0.619 mm-1, F(000) = 1088, the final R = 0.0396 and wR = 0.0945 for 4394 observed reflections (I > 2σ(I)). Compound 5 crystallizes in orthorhombic system, space group P21212 as well, with parameters of a = 11.9875(15), b = 19.651(2), c = 7.2163(9) Å, Z = 2, V = 1699.9(3) Å3, Mr = 582.83, Dc = 1.139 g/cm-1, S = 1.091, μ = 0.070 mm-1, F(000) = 636, the final R = 0.0653 and wR = 0.0719 for 1518 observed reflections (I > 2σ(I)). Additionally, electrochemical properties of compounds 3 and 4 have been investigated by the cyclic and differential pulse voltammogram techniques.
Three title compounds (3~5) have been successfully synthesized via interactive reactions between ferrocenecarboxylic and dehydroabietic acids, which can be characterized by FT-IR, elemental analysis, ESI-MS, and NMR spectroscopy. The crystal structures of compounds 4 and 5 can be determined by single-crystal X-ray diffraction. Compound 4 is of orthorhombic system, space group P212121 with a = 7.7010(5), b = 11.7542(9), c = 28.3173(18) Å, Z = 4, V = 2563.3(3) Å3, Mr = 512.45, Dc = 1.328 g/cm-1, S = 1.041, μ = 0.619 mm-1, F(000) = 1088, the final R = 0.0396 and wR = 0.0945 for 4394 observed reflections (I > 2σ(I)). Compound 5 crystallizes in orthorhombic system, space group P21212 as well, with parameters of a = 11.9875(15), b = 19.651(2), c = 7.2163(9) Å, Z = 2, V = 1699.9(3) Å3, Mr = 582.83, Dc = 1.139 g/cm-1, S = 1.091, μ = 0.070 mm-1, F(000) = 636, the final R = 0.0653 and wR = 0.0719 for 1518 observed reflections (I > 2σ(I)). Additionally, electrochemical properties of compounds 3 and 4 have been investigated by the cyclic and differential pulse voltammogram techniques.
2020, 39(3): 588-597
doi: 10.14102/j.cnki.0254–5861.2011–2733
Abstract:
Ag2O/TiO2 heterostructure has been constructed by loading corner-truncated cubic Ag2O on the TiO2 hollow nanofibers via an electrospinning-precipitation method. Compared to individual Ag2O and TiO2, Ag2O/TiO2 heterostructure exhibits obviously enhanced photocatalytic activity for the photodegradation of methyl orange (MO) under visible light irradiation. The composite with molar ratio of Ag2O to TiO2 at 4:10 exhibits the best photocatalytic performance with MO degraded 93% in 6 min. The superior activity is mainly attributed to the surface plasmon resonance (SPR) effect of metallic Ag in-situ produced during the photocatalytic process, which can favor electron transfer to the conduction band of TiO2. This leads to the efficient separation of photogenerated carriers, thus a superior photodegradation activity. Moreover, the energy band alignments of Ag2O/TiO2 heterostructure are calculated, which provides strong support for the proposed mechanism.
Ag2O/TiO2 heterostructure has been constructed by loading corner-truncated cubic Ag2O on the TiO2 hollow nanofibers via an electrospinning-precipitation method. Compared to individual Ag2O and TiO2, Ag2O/TiO2 heterostructure exhibits obviously enhanced photocatalytic activity for the photodegradation of methyl orange (MO) under visible light irradiation. The composite with molar ratio of Ag2O to TiO2 at 4:10 exhibits the best photocatalytic performance with MO degraded 93% in 6 min. The superior activity is mainly attributed to the surface plasmon resonance (SPR) effect of metallic Ag in-situ produced during the photocatalytic process, which can favor electron transfer to the conduction band of TiO2. This leads to the efficient separation of photogenerated carriers, thus a superior photodegradation activity. Moreover, the energy band alignments of Ag2O/TiO2 heterostructure are calculated, which provides strong support for the proposed mechanism.
