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2022 Volume 38 Issue 12
2022, 38(12): 2321-2341
doi: 10.11862/CJIC.2022.254
Abstract:
Alkyne carbon material is a novel two-dimensional carbon allotrope with good electrical conductivity and high specific surface area. The porous structure composed of sp2- and sp-hybridized carbon promotes charge transfer and ion transport, which endows alkyne carbon material with broad application prospects in the field of energy storage and conversion. Theoretically, γ-graphyne (γ-GY) has the highest stability among the γ-GY-like carbon materials due to its stable conjugated system and unique triangular pore structure, which promotes the ionic intercalation/ de-intercalation process in alkali metal ion batteries. Given its excellent semiconductor properties, γ-GY is also an ideal candidate for photoelectrochemical and photocatalytic oxygen evolution and hydrogen evolution. Besides, the molecular framework and electron configuration of γ-GY can be regulated by heteroatom doping or rational molecular structural design of organic precursors. This review summarized synthesis methods of γ-GY and its applications in lithium (sodium and potassium) ion batteries, electrocatalysis, and photocatalysis, then further proposed the challenges and opportunities in the energy field.
Alkyne carbon material is a novel two-dimensional carbon allotrope with good electrical conductivity and high specific surface area. The porous structure composed of sp2- and sp-hybridized carbon promotes charge transfer and ion transport, which endows alkyne carbon material with broad application prospects in the field of energy storage and conversion. Theoretically, γ-graphyne (γ-GY) has the highest stability among the γ-GY-like carbon materials due to its stable conjugated system and unique triangular pore structure, which promotes the ionic intercalation/ de-intercalation process in alkali metal ion batteries. Given its excellent semiconductor properties, γ-GY is also an ideal candidate for photoelectrochemical and photocatalytic oxygen evolution and hydrogen evolution. Besides, the molecular framework and electron configuration of γ-GY can be regulated by heteroatom doping or rational molecular structural design of organic precursors. This review summarized synthesis methods of γ-GY and its applications in lithium (sodium and potassium) ion batteries, electrocatalysis, and photocatalysis, then further proposed the challenges and opportunities in the energy field.
2022, 38(12): 2342-2362
doi: 10.11862/CJIC.2022.252
Abstract:
Defect engineering is an effective strategy for modulating the structure of metal-organic frameworks (MOFs) to boost their performance in water treatment. The defect can be formed when the regular periodic arrangement of atoms or ions in the crystalline parent framework is broken due to the missing or dislocation of atoms or ions. In the field of defective MOFs, the types of defects are divided into (ⅰ) missing linker defects, (ⅱ) modified linker defects, (ⅲ) missing node defects, and (ⅳ) modified node defects. Although the construction of defective MOFs has received continuous attention, which remains challenging today. Up to now, there are two synthetic pathways to fabricate defective MOFs: the modulation during the synthesis process and the post-synthetic treatment methods. Specifically, defective MOFs can be fabricated by adjusting the synthesis conditions (temperature, the ratio of metal/ligand, etc.), introducing modulators, thermal activation, metal node substitution, and so on. Many advanced techniques like X-ray diffraction (XRD), specific surface area analysis, thermogravimetric analyses-differential scanning calorimetry (TGA-DSC), electron paramagnetic resonance (EPR), X-ray photoelectron spectra (XPS), high-resolution transmission electron microscopy (HR-TEM), spherical aberration-corrected transmission electron microscope (AC-TEM), and X-ray absorption spectroscopy (XAS) can effectively affirm the defective structure of MOFs. In the field of water remediation, the construction of defective MOFs can boost their performance of advanced oxidation processes like photocatalysis, persulfate (PS) activation, and photo-Fenton by enhancing separation rates of photoinduced electron-hole, promoting the photoelectron transfer and narrowing the band gap compared with pristine MOFs. Moreover, because the defective sites are introduced in the framework, they act as dominant active sites in the PS system, promoting the generation of radicals and creating a nonradical degradation pathway. Meanwhile, defective MOFs with rich unsaturated coordination centers can provide more adsorption sites toward pollutants, further enhancing the adsorption capacities and rates of sorbents. This review summarized the fabrications, characterizations, and applications in the water treatment of defective MOFs. Meanwhile, the prospects of defective MOFs for pollutant removal from water are proposed in this review.
Defect engineering is an effective strategy for modulating the structure of metal-organic frameworks (MOFs) to boost their performance in water treatment. The defect can be formed when the regular periodic arrangement of atoms or ions in the crystalline parent framework is broken due to the missing or dislocation of atoms or ions. In the field of defective MOFs, the types of defects are divided into (ⅰ) missing linker defects, (ⅱ) modified linker defects, (ⅲ) missing node defects, and (ⅳ) modified node defects. Although the construction of defective MOFs has received continuous attention, which remains challenging today. Up to now, there are two synthetic pathways to fabricate defective MOFs: the modulation during the synthesis process and the post-synthetic treatment methods. Specifically, defective MOFs can be fabricated by adjusting the synthesis conditions (temperature, the ratio of metal/ligand, etc.), introducing modulators, thermal activation, metal node substitution, and so on. Many advanced techniques like X-ray diffraction (XRD), specific surface area analysis, thermogravimetric analyses-differential scanning calorimetry (TGA-DSC), electron paramagnetic resonance (EPR), X-ray photoelectron spectra (XPS), high-resolution transmission electron microscopy (HR-TEM), spherical aberration-corrected transmission electron microscope (AC-TEM), and X-ray absorption spectroscopy (XAS) can effectively affirm the defective structure of MOFs. In the field of water remediation, the construction of defective MOFs can boost their performance of advanced oxidation processes like photocatalysis, persulfate (PS) activation, and photo-Fenton by enhancing separation rates of photoinduced electron-hole, promoting the photoelectron transfer and narrowing the band gap compared with pristine MOFs. Moreover, because the defective sites are introduced in the framework, they act as dominant active sites in the PS system, promoting the generation of radicals and creating a nonradical degradation pathway. Meanwhile, defective MOFs with rich unsaturated coordination centers can provide more adsorption sites toward pollutants, further enhancing the adsorption capacities and rates of sorbents. This review summarized the fabrications, characterizations, and applications in the water treatment of defective MOFs. Meanwhile, the prospects of defective MOFs for pollutant removal from water are proposed in this review.
2022, 38(12): 2363-2371
doi: 10.11862/CJIC.2022.244
Abstract:
It remains a challenge in the preparation of multifunctional conductive gels which combine self-healing and the ability to respond to complex environments. In this work, a new ionic self-healing gel DPZI with the properties of photochromic, conductive, self-adhesive, and wide temperature working range was prepared by polymerization of acrylic acid with the addition of 4, 4'-(perfluorocyclopentene-1, 2-diyl)bis(5-methylthiophene-2-carbaldehyde) (DEA) and 1-butyl-3-methylimidazolium tetrafluoroborate ((BMIm)BF4) ionic liquids. Owing to the high thermal stability and low vapor pressure of (BMIm)BF4, the obtained DPZI gel exhibited good mechanical properties in a wide temperature range from-20 to 40 ℃ and high ionic conductivity. The dynamic coordination bond formed by Zn2+ and—COO- introduced in the DPZI system enabled the gel to possess rapid self-healing ability and ultra-fast resistive response recovery in 0.06 s. The gel displayed excellent anti-freezing properties due to the combination of ionic liquids. DPZI exhibited a rapid reversible yellow-blue color transition within 10 s due to the isomerization of the photochromic unit DEA, and the open-loop form/closed-loop form isomerization of the photochromic unit also enabled the regulation of gel conductivity. Additionally, it showed good cycling stability with minor resistance fluctuations over 50 stretch-release cycles. Given its superior performance, the DPZI gel could effectively detect and distinguish human motions, such as the bending and stretching of a finger, knee, neck, or elbow joint, with a rapid and reliable signal response (strain sensitivity of 0.2%).
It remains a challenge in the preparation of multifunctional conductive gels which combine self-healing and the ability to respond to complex environments. In this work, a new ionic self-healing gel DPZI with the properties of photochromic, conductive, self-adhesive, and wide temperature working range was prepared by polymerization of acrylic acid with the addition of 4, 4'-(perfluorocyclopentene-1, 2-diyl)bis(5-methylthiophene-2-carbaldehyde) (DEA) and 1-butyl-3-methylimidazolium tetrafluoroborate ((BMIm)BF4) ionic liquids. Owing to the high thermal stability and low vapor pressure of (BMIm)BF4, the obtained DPZI gel exhibited good mechanical properties in a wide temperature range from-20 to 40 ℃ and high ionic conductivity. The dynamic coordination bond formed by Zn2+ and—COO- introduced in the DPZI system enabled the gel to possess rapid self-healing ability and ultra-fast resistive response recovery in 0.06 s. The gel displayed excellent anti-freezing properties due to the combination of ionic liquids. DPZI exhibited a rapid reversible yellow-blue color transition within 10 s due to the isomerization of the photochromic unit DEA, and the open-loop form/closed-loop form isomerization of the photochromic unit also enabled the regulation of gel conductivity. Additionally, it showed good cycling stability with minor resistance fluctuations over 50 stretch-release cycles. Given its superior performance, the DPZI gel could effectively detect and distinguish human motions, such as the bending and stretching of a finger, knee, neck, or elbow joint, with a rapid and reliable signal response (strain sensitivity of 0.2%).
2022, 38(12): 2372-2382
doi: 10.11862/CJIC.2022.249
Abstract:
Compound [Zn2(C13H17NO3)2]n (1) was synthesized by a traditional solvothermal method with L-isoleucine derived ligand (C13H19NO3) and Zn(NO3)2·6H2O as a coordination polymer. Single-crystal X-ray diffraction results show that compound 1 crystallizes in the monoclinic crystal system with the P21 space group. The ligands bridge the metal ions to form a 2D layer structure, which further forms a 3D supramolecular network through van der Waals forces between the adjacent layers. The addition of rhodamine B (Rho-B) into the synthetic process of compound 1 leads to a composite material 2. The fluorescence test results showed that the luminescence of compound 1 was mainly based on the ligand under the excitation at 370 nm, while composite 2 showed the additional emission peak of Rho-B at 580 nm besides the ligand. Using the relative intensity ratios of emission peaks (the ligand and Rho-B) as the detection signal, composite 2 was applied to the detection of metal cations and volatile organic compounds (VOCs). The experimental results showed that the material could selectively recognize Cr3+ in H2O and demonstrate a quick response to the benzaldehyde vapor.
Compound [Zn2(C13H17NO3)2]n (1) was synthesized by a traditional solvothermal method with L-isoleucine derived ligand (C13H19NO3) and Zn(NO3)2·6H2O as a coordination polymer. Single-crystal X-ray diffraction results show that compound 1 crystallizes in the monoclinic crystal system with the P21 space group. The ligands bridge the metal ions to form a 2D layer structure, which further forms a 3D supramolecular network through van der Waals forces between the adjacent layers. The addition of rhodamine B (Rho-B) into the synthetic process of compound 1 leads to a composite material 2. The fluorescence test results showed that the luminescence of compound 1 was mainly based on the ligand under the excitation at 370 nm, while composite 2 showed the additional emission peak of Rho-B at 580 nm besides the ligand. Using the relative intensity ratios of emission peaks (the ligand and Rho-B) as the detection signal, composite 2 was applied to the detection of metal cations and volatile organic compounds (VOCs). The experimental results showed that the material could selectively recognize Cr3+ in H2O and demonstrate a quick response to the benzaldehyde vapor.
2022, 38(12): 2383-2391
doi: 10.11862/CJIC.2022.240
Abstract:
Two amphiphilic porphyrin-ruthenium (Ⅱ) complexes PorRu and PorZn-Ru were synthesized by the coordination of metal Ru(Ⅱ) and porphyrin-phenanthroline ligand L which is modified with conjugated pyrazine ring at the β position of porphyrin. Two compounds were characterized and evaluated by NMR and mass spectrometry, linear and nonlinear spectral analysis, and photodynamic anti-cancer activity study. Experimental results show that the two compounds had very high 1O2 quantum yields (0.93, 0.82), high two-photon absorption cross-sections (619, 621 GM), and up to about 22 nmol per 106 cell uptakes of nasopharyngeal carcinoma HK-1 cell line. Although no obvious subcellular target was observed by the costaining cell images, the high 1O2 yields and good cellular uptakes still made the ruthenium compounds have good photodynamic anticancer activity against HK-1 cells. At the light dose of 2 J·cm-2 and the administration concentration of 4 μmol·L-1, the inhibition efficiency reached (87.44±2.21)% and (45.03±2.85)% respectively.
Two amphiphilic porphyrin-ruthenium (Ⅱ) complexes PorRu and PorZn-Ru were synthesized by the coordination of metal Ru(Ⅱ) and porphyrin-phenanthroline ligand L which is modified with conjugated pyrazine ring at the β position of porphyrin. Two compounds were characterized and evaluated by NMR and mass spectrometry, linear and nonlinear spectral analysis, and photodynamic anti-cancer activity study. Experimental results show that the two compounds had very high 1O2 quantum yields (0.93, 0.82), high two-photon absorption cross-sections (619, 621 GM), and up to about 22 nmol per 106 cell uptakes of nasopharyngeal carcinoma HK-1 cell line. Although no obvious subcellular target was observed by the costaining cell images, the high 1O2 yields and good cellular uptakes still made the ruthenium compounds have good photodynamic anticancer activity against HK-1 cells. At the light dose of 2 J·cm-2 and the administration concentration of 4 μmol·L-1, the inhibition efficiency reached (87.44±2.21)% and (45.03±2.85)% respectively.
2022, 38(12): 2392-2400
doi: 10.11862/CJIC.2022.242
Abstract:
In this paper, a simple calcination process was used to synthesize nanocrystalline cobalt boride (CoB), which was employed to catalyze the hydrolysis of ammonia borane solution at room temperature. Specifically, it was found that the CoB exhibited high performance with a turnover frequency (TOF) of 35.3 molH2·molcat-1·min-1, which is superior to platinum (TOF=29.3 molH2·molcat-1·min-1). It still possessed excellent catalytic hydrogen production performance after repeated testing for 8 times. We found that Co0 species on the surface of CoB is a possible catalytic active site, and the boron site on the surface can effectively assist the Co0 site to achieve the synergistic catalytic hydrogen production from ammonia borane.
In this paper, a simple calcination process was used to synthesize nanocrystalline cobalt boride (CoB), which was employed to catalyze the hydrolysis of ammonia borane solution at room temperature. Specifically, it was found that the CoB exhibited high performance with a turnover frequency (TOF) of 35.3 molH2·molcat-1·min-1, which is superior to platinum (TOF=29.3 molH2·molcat-1·min-1). It still possessed excellent catalytic hydrogen production performance after repeated testing for 8 times. We found that Co0 species on the surface of CoB is a possible catalytic active site, and the boron site on the surface can effectively assist the Co0 site to achieve the synergistic catalytic hydrogen production from ammonia borane.
2022, 38(12): 2401-2411
doi: 10.11862/CJIC.2022.230
Abstract:
Ultrastable Y-type (USY) zeolite catalysts with high acid content and high hydrothermal stability (USY-c-w) were obtained by crystallizing an industrial USY-zeolite in a traditional hydrothermal system with the help of a surfactant cetyltrimethylammonium bromide (CTABr). The physicochemical properties of as-synthesized USY-zeolite samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), solid-state NMR, N2 adsorption-desorption, ammonia temperature programmed desorption (NH3-TPD), FT-IR, and pyridine infrared spectroscopy (Py-IR). Catalytic cracking of 1, 3, 5-triisopropylbenzene (TIPB) was selected as a probe reaction to investigate the catalytic performance of as-synthesized catalysts and compare it with that of the industrial USY-zeolite. The results exhibited that after hydrothermal re-crystallization, the framework of USY-zeolite suffered from a partial reformation. Desilicication by steam or alkali treatment results in the formation of a large number of silanol nests, which reacts with Al species resulting from the non-framework aluminum in the USY-zeolite and then promotes the formation of the"new"framework Al. This offers as-synthesized sample with a less Si/Al ratio (nSi/nAl) and with increasing acid sites. The increased Al content in the zeolite framework was confirmed by the results of XRD, FTIR, X-ray energy dispersive spectrum (EDS), and NMR. For example, the framework Si/Al ratio decreased from 10 (industrial USY-zeolite) to 3.0 (USY-045-07C). The NH3-TPD experiment and Py-IR provided direct evidence supporting the increased acidity in as-synthesized catalysts. Moreover, the results obtained by the N2 adsorption-desorption experiment, SEM, and TEM also showed that abundant mesopores were also introduced into as-synthesized samples with more weak acid sites along with more medium-strong acid ones. During the catalytic cracking of TIPB, as-synthesized USY-c-w showed more excellent catalytic performance with higher conversion of TIPB than the reference sample.
Ultrastable Y-type (USY) zeolite catalysts with high acid content and high hydrothermal stability (USY-c-w) were obtained by crystallizing an industrial USY-zeolite in a traditional hydrothermal system with the help of a surfactant cetyltrimethylammonium bromide (CTABr). The physicochemical properties of as-synthesized USY-zeolite samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), solid-state NMR, N2 adsorption-desorption, ammonia temperature programmed desorption (NH3-TPD), FT-IR, and pyridine infrared spectroscopy (Py-IR). Catalytic cracking of 1, 3, 5-triisopropylbenzene (TIPB) was selected as a probe reaction to investigate the catalytic performance of as-synthesized catalysts and compare it with that of the industrial USY-zeolite. The results exhibited that after hydrothermal re-crystallization, the framework of USY-zeolite suffered from a partial reformation. Desilicication by steam or alkali treatment results in the formation of a large number of silanol nests, which reacts with Al species resulting from the non-framework aluminum in the USY-zeolite and then promotes the formation of the"new"framework Al. This offers as-synthesized sample with a less Si/Al ratio (nSi/nAl) and with increasing acid sites. The increased Al content in the zeolite framework was confirmed by the results of XRD, FTIR, X-ray energy dispersive spectrum (EDS), and NMR. For example, the framework Si/Al ratio decreased from 10 (industrial USY-zeolite) to 3.0 (USY-045-07C). The NH3-TPD experiment and Py-IR provided direct evidence supporting the increased acidity in as-synthesized catalysts. Moreover, the results obtained by the N2 adsorption-desorption experiment, SEM, and TEM also showed that abundant mesopores were also introduced into as-synthesized samples with more weak acid sites along with more medium-strong acid ones. During the catalytic cracking of TIPB, as-synthesized USY-c-w showed more excellent catalytic performance with higher conversion of TIPB than the reference sample.
2022, 38(12): 2412-2422
doi: 10.11862/CJIC.2022.217
Abstract:
A series of 15%Ni-5%M/γ-Al2O3 catalysts (denoted as NMA, M=Na, Mg, Ce) modified by Alkali metal Na, alkaline-earth metal Mg, and rare earth metal Ce promoters were prepared by the incipient-wetness co-impregnation method. The texture and surface properties of the above catalysts were characterized and analyzed by XRD (X-ray diffraction), N2 adsorption-desorption, H2-TPR (H2-programmed temperature reduction), TEM (transmission electron microscope), NH3-TPD (NH3-programmed temperature desorption), TG (thermogravimetric), and Raman spectrum techniques. Effects of these promoters on the catalytic performance for steam reforming of JP-10 as a representative of polycyclic hydrocarbons were investigated in a micro-channel reactor (length: 300 mm, inner diameter: 4 mm, 304 stainless steel) wash-coated by catalyst slurry from 600 to 750 ℃ with the feeds of exo-tetrahydrodicyclopentadi-enew (JP-10) (0.5 mL·min-1) and deionized water (1.5 mL·min-1). The above catalyst slurry was prepared by fast ball-milling of catalyst powder, deionized water, 25% silica sol binder for 0.5 h, and the resulted catalyst loading was about 0.25 g. The results showed that all the promoters significantly improved the catalytic activity of Ni/γ -Al2O3 catalysts (denoted as NA) and carbon deposition resistance. Among them, the alkali metal promoter Na exhibited the best modification effect overall. It not only reduced the size of nickel grains and total acid amount, improved the dispersibility of nickel active components, and reduced property, but also inhibited the accumulation of nickel in the high-temperature reforming reaction to the maximum extent. Specifically, conversion of JP-10 and H2 selectivity of NNaA catalyst could reach 82.9% and 73.3%, respectively, and the carbon formation was as low as 0.53 mg·gfeed-1 under the reaction conditions of normal pressure, 750 ℃, steam/carbon (S/C) molar ratio of 2.4, and weight hourly space velocity (WHSV) of 472 h-1. After the reaction, most filamentous carbons were observed on catalysts NNaA, while carbon deposits on the other catalysts were mostly amorphous carbons.
A series of 15%Ni-5%M/γ-Al2O3 catalysts (denoted as NMA, M=Na, Mg, Ce) modified by Alkali metal Na, alkaline-earth metal Mg, and rare earth metal Ce promoters were prepared by the incipient-wetness co-impregnation method. The texture and surface properties of the above catalysts were characterized and analyzed by XRD (X-ray diffraction), N2 adsorption-desorption, H2-TPR (H2-programmed temperature reduction), TEM (transmission electron microscope), NH3-TPD (NH3-programmed temperature desorption), TG (thermogravimetric), and Raman spectrum techniques. Effects of these promoters on the catalytic performance for steam reforming of JP-10 as a representative of polycyclic hydrocarbons were investigated in a micro-channel reactor (length: 300 mm, inner diameter: 4 mm, 304 stainless steel) wash-coated by catalyst slurry from 600 to 750 ℃ with the feeds of exo-tetrahydrodicyclopentadi-enew (JP-10) (0.5 mL·min-1) and deionized water (1.5 mL·min-1). The above catalyst slurry was prepared by fast ball-milling of catalyst powder, deionized water, 25% silica sol binder for 0.5 h, and the resulted catalyst loading was about 0.25 g. The results showed that all the promoters significantly improved the catalytic activity of Ni/γ -Al2O3 catalysts (denoted as NA) and carbon deposition resistance. Among them, the alkali metal promoter Na exhibited the best modification effect overall. It not only reduced the size of nickel grains and total acid amount, improved the dispersibility of nickel active components, and reduced property, but also inhibited the accumulation of nickel in the high-temperature reforming reaction to the maximum extent. Specifically, conversion of JP-10 and H2 selectivity of NNaA catalyst could reach 82.9% and 73.3%, respectively, and the carbon formation was as low as 0.53 mg·gfeed-1 under the reaction conditions of normal pressure, 750 ℃, steam/carbon (S/C) molar ratio of 2.4, and weight hourly space velocity (WHSV) of 472 h-1. After the reaction, most filamentous carbons were observed on catalysts NNaA, while carbon deposits on the other catalysts were mostly amorphous carbons.
2022, 38(12): 2423-2432
doi: 10.11862/CJIC.2022.243
Abstract:
In this work, Ti3 AlC2 was etched and exfoliated into few-layer of Ti3C2Tx MXene nanosheets using wet etching. Then, dendritic Co was prepared by electrochemical reduction, and afterwards Ti3C2Tx/dendritic Co/PVDF composite photothermal membrane was prepared by vacuum filtration utilizing hydrophilic polyvinylidene fluoride (PVDF) membrane as substrate. The structure and morphology of the composites were characterized, as well as the optical absorption and interfacial evaporation properties of the composite photothermal membrane were studied. The results displayed that under the simulated one solar light (the light intensity was 1 kW·m-2), the light absorptivity of Ti3C2Tx/dendritic Co/PVDF composite photothermal membrane was 95.3%, the evaporation rate of pure water reached 1.78 kg·m-2·h-1, and the efficiency of interface evaporation was as high as 97.5%. In addition, the performance of interfacial evaporation in simulated seawater was accordingly tested. The water obtained by evaporation and condensation meets the drinking water standards of World Health Organization (WHO) and U.S. Environmental Protection Agency (EPA), and the evaporation rate reached 1.61 kg·m-2·h-1, which was stable at 1.59 kg·m-2·h-1 after five cycles.
In this work, Ti3 AlC2 was etched and exfoliated into few-layer of Ti3C2Tx MXene nanosheets using wet etching. Then, dendritic Co was prepared by electrochemical reduction, and afterwards Ti3C2Tx/dendritic Co/PVDF composite photothermal membrane was prepared by vacuum filtration utilizing hydrophilic polyvinylidene fluoride (PVDF) membrane as substrate. The structure and morphology of the composites were characterized, as well as the optical absorption and interfacial evaporation properties of the composite photothermal membrane were studied. The results displayed that under the simulated one solar light (the light intensity was 1 kW·m-2), the light absorptivity of Ti3C2Tx/dendritic Co/PVDF composite photothermal membrane was 95.3%, the evaporation rate of pure water reached 1.78 kg·m-2·h-1, and the efficiency of interface evaporation was as high as 97.5%. In addition, the performance of interfacial evaporation in simulated seawater was accordingly tested. The water obtained by evaporation and condensation meets the drinking water standards of World Health Organization (WHO) and U.S. Environmental Protection Agency (EPA), and the evaporation rate reached 1.61 kg·m-2·h-1, which was stable at 1.59 kg·m-2·h-1 after five cycles.
2022, 38(12): 2433-2442
doi: 10.11862/CJIC.2022.250
Abstract:
SnBi alloy was prepared by the two-step electrodeposition method. Sn was first electrodeposited on the carbon cloth (CC). Since the electrolyte used in the second step was acidic, Sn was dissolved in the electrolyte to form a small amount of Sn2+. As a result, SnBi alloy dendrites formed by doping a small amount of Sn with Bi. Subsequently, SnBi alloy dendrites were transformed into SnBi alloy nanoparticles (NPs) by in-situ chemical oxidation and electrochemical reduction. Thanks to the nucleation sites provided by Sn, SnBi dendrites grow densely and uniformly on the CC, providing a high-quality precursor and finally achieving SnBi nanoparticles with a diameter of about 20 nm through two-step transformation. CC/Sn/SnBi NPs electrode exhibited 94.9% formate selectivity and current density up to 36 mA·cm-2 at -1.08 V (vs RHE), showing high activity of electrocatalytic reduction of CO2 with the continuous 12 h stability.
SnBi alloy was prepared by the two-step electrodeposition method. Sn was first electrodeposited on the carbon cloth (CC). Since the electrolyte used in the second step was acidic, Sn was dissolved in the electrolyte to form a small amount of Sn2+. As a result, SnBi alloy dendrites formed by doping a small amount of Sn with Bi. Subsequently, SnBi alloy dendrites were transformed into SnBi alloy nanoparticles (NPs) by in-situ chemical oxidation and electrochemical reduction. Thanks to the nucleation sites provided by Sn, SnBi dendrites grow densely and uniformly on the CC, providing a high-quality precursor and finally achieving SnBi nanoparticles with a diameter of about 20 nm through two-step transformation. CC/Sn/SnBi NPs electrode exhibited 94.9% formate selectivity and current density up to 36 mA·cm-2 at -1.08 V (vs RHE), showing high activity of electrocatalytic reduction of CO2 with the continuous 12 h stability.
2022, 38(12): 2443-2451
doi: 10.11862/CJIC.2022.218
Abstract:
Five bis(substituted salicylaldehyde) m-phthaloylhydrazone organotin complexes, m-Ph(CONH—N=CH (o-O)PhR1)(SnR2)2, were synthesized by one-pot solvothermal reaction of benzene-1, 3-dicarbohydrazide, substituted salicylaldehydes and organotin precursors, respectively, where R1=Naphth, R2=Cy (1); R1=3-t-Bu, R2=n-Bu (2); R1= 5-F, R2 =Ph (3); R1=4-Cl, R2=Ph (4); R1=3-t-Bu, R2=Ph (5). Their structures were characterized by elemental analysis, IR and 1H, 13C, 119Sn NMR, and the crystal structures of complexes 1-5 were confirmed by X-ray diffraction. Complexes 1-4 belong to the triclinic P1 space group and complex 5 crystallizes in the monoclinic P21 space group. The central tin and the coordinated atom form a five-coordinated distorted triangular bipyramids configuration. By C1—C2 or C4—C8 single bond rotation, the configuration of the two coordination chains on the central benzene ring is reversed. Here, it is defined that the configuration of salicylaldehyde acylhydrazone chain coordinated with organotin to form far from the central benzene ring is called"trans", and the configuration with the same orientation as the central benzene ring is called"cis". Therefore, complex 1 forms a"trans-trans"configuration, complex 2 forms a"cis-cis "configuration, and complexes 3, 4 and 5 form a"cis-trans"configuration. Fluorescence studies showed that the complexes had luminescence properties, especially the organic solutions of 1 and 4 had strong fluorescence properties.
Five bis(substituted salicylaldehyde) m-phthaloylhydrazone organotin complexes, m-Ph(CONH—N=CH (o-O)PhR1)(SnR2)2, were synthesized by one-pot solvothermal reaction of benzene-1, 3-dicarbohydrazide, substituted salicylaldehydes and organotin precursors, respectively, where R1=Naphth, R2=Cy (1); R1=3-t-Bu, R2=n-Bu (2); R1= 5-F, R2 =Ph (3); R1=4-Cl, R2=Ph (4); R1=3-t-Bu, R2=Ph (5). Their structures were characterized by elemental analysis, IR and 1H, 13C, 119Sn NMR, and the crystal structures of complexes 1-5 were confirmed by X-ray diffraction. Complexes 1-4 belong to the triclinic P1 space group and complex 5 crystallizes in the monoclinic P21 space group. The central tin and the coordinated atom form a five-coordinated distorted triangular bipyramids configuration. By C1—C2 or C4—C8 single bond rotation, the configuration of the two coordination chains on the central benzene ring is reversed. Here, it is defined that the configuration of salicylaldehyde acylhydrazone chain coordinated with organotin to form far from the central benzene ring is called"trans", and the configuration with the same orientation as the central benzene ring is called"cis". Therefore, complex 1 forms a"trans-trans"configuration, complex 2 forms a"cis-cis "configuration, and complexes 3, 4 and 5 form a"cis-trans"configuration. Fluorescence studies showed that the complexes had luminescence properties, especially the organic solutions of 1 and 4 had strong fluorescence properties.
2022, 38(12): 2452-2458
doi: 10.11862/CJIC.2022.247
Abstract:
The composite catalyst of CuPd alloy nanoparticles supported on MgO (CuPd/MgO) was prepared by an impregnation reduction method. CuPd/MgO showed excellent catalytic performance during formaldehyde reforming for hydrogen production at room temperature in the air. The turnover frequency (TOF) of CuPd/MgO was as high as 812.6 h-1, which was respectively 2.3 times and 23 times higher than that of Cu/MgO (TOF=356.7 h-1) and Pd/MgO (TOF=34.8 h-1) under the same reaction conditions. Based on the experimental observations and characterization results, we found that a strong metal support interaction (SMSI) between CuPd alloy nanoparticles and MgO support enriched with defects on the surface was present in CuPd/MgO. This interaction was conducive to the transfer and recombination of electrons on the catalyst, greatly promoting the adsorption, activation, and reduction of oxygen on the catalyst surface to form superoxide anion radical (·O2-). The ·O2- combined with the proton generated by the C—H bond breaking of formaldehyde to form superoxide radical (·OOH). The hydrogen radical (·H) dissociated from water molecules in the reaction system continuously combined with ·OOH to generate hydrogen and oxygen, leading to the generation of hydrogen and the regeneration of oxygen.
The composite catalyst of CuPd alloy nanoparticles supported on MgO (CuPd/MgO) was prepared by an impregnation reduction method. CuPd/MgO showed excellent catalytic performance during formaldehyde reforming for hydrogen production at room temperature in the air. The turnover frequency (TOF) of CuPd/MgO was as high as 812.6 h-1, which was respectively 2.3 times and 23 times higher than that of Cu/MgO (TOF=356.7 h-1) and Pd/MgO (TOF=34.8 h-1) under the same reaction conditions. Based on the experimental observations and characterization results, we found that a strong metal support interaction (SMSI) between CuPd alloy nanoparticles and MgO support enriched with defects on the surface was present in CuPd/MgO. This interaction was conducive to the transfer and recombination of electrons on the catalyst, greatly promoting the adsorption, activation, and reduction of oxygen on the catalyst surface to form superoxide anion radical (·O2-). The ·O2- combined with the proton generated by the C—H bond breaking of formaldehyde to form superoxide radical (·OOH). The hydrogen radical (·H) dissociated from water molecules in the reaction system continuously combined with ·OOH to generate hydrogen and oxygen, leading to the generation of hydrogen and the regeneration of oxygen.
2022, 38(12): 2459-2468
doi: 10.11862/CJIC.2022.256
Abstract:
Herein, a flexible ultramicroporous metal-organic framework {[Co(DTBDA)]·4H2O}n (FJI-H35) was prepared from a semirigid ligand 3', 5'-di(1H-1, 2, 4-triazol-1-yl)-(1, 1'-biphenyl)-3, 5-dicarboxylic acid (H2DTBDA) and cobalt nitrate. After activation, FJI-H35 underwent an adaptive structural transformation, making the pore diameter shrink from 0.43 to 0.37 nm. Gas adsorption tests showed that FJI-H35 could selectively capture CO2 from N2 and CH4 with a high adsorption selectivity of 178 and a relatively low adsorption enthalpy (28.2 kJ·mol-1). Breakthrough experiments further confirmed that FJI-H35 could efficiently and selectively capture CO2 from CO2/N2 (15∶85, V/V) and CO2/CH4 (50∶50, V/V) mixtures.
Herein, a flexible ultramicroporous metal-organic framework {[Co(DTBDA)]·4H2O}n (FJI-H35) was prepared from a semirigid ligand 3', 5'-di(1H-1, 2, 4-triazol-1-yl)-(1, 1'-biphenyl)-3, 5-dicarboxylic acid (H2DTBDA) and cobalt nitrate. After activation, FJI-H35 underwent an adaptive structural transformation, making the pore diameter shrink from 0.43 to 0.37 nm. Gas adsorption tests showed that FJI-H35 could selectively capture CO2 from N2 and CH4 with a high adsorption selectivity of 178 and a relatively low adsorption enthalpy (28.2 kJ·mol-1). Breakthrough experiments further confirmed that FJI-H35 could efficiently and selectively capture CO2 from CO2/N2 (15∶85, V/V) and CO2/CH4 (50∶50, V/V) mixtures.
2022, 38(12): 2469-2478
doi: 10.11862/CJIC.2022.237
Abstract:
Two novel metal-organic macrocycles (MFe and MCu) were constructed using the flexible and redox-active ferrocene ligand. The macrocycles effectively quenched the fluorescence of organic dyes and exhibited the capability to trigger the photoinduced electron transfer. Due to relatively lower reduction potentials, MCu exhibited better catalytic features for proton reduction and could better catalyze the reduction of nitro compounds. The large size of the substrates leads to a decreased efficiency in the nitro reduction process. The Michaelis-Menten mechanism was used to verify the photocatalytic system, which revealed the importance of the interaction between substrate and catalyst.
Two novel metal-organic macrocycles (MFe and MCu) were constructed using the flexible and redox-active ferrocene ligand. The macrocycles effectively quenched the fluorescence of organic dyes and exhibited the capability to trigger the photoinduced electron transfer. Due to relatively lower reduction potentials, MCu exhibited better catalytic features for proton reduction and could better catalyze the reduction of nitro compounds. The large size of the substrates leads to a decreased efficiency in the nitro reduction process. The Michaelis-Menten mechanism was used to verify the photocatalytic system, which revealed the importance of the interaction between substrate and catalyst.
2022, 38(12): 2479-2490
doi: 10.11862/CJIC.2022.238
Abstract:
Three Zn(Ⅱ)-based metal-organic frameworks with V-shaped ligands, namely {[Zn2(BIDPS)2(OBA)2]·DMA}n (1), {[Zn(BIDPT)(PA)]·DMF}n (2), and {[Zn(BIDPS)(PA)(H2O)2]·2H2O}n (3) (BIDPS =4, 4'-bis(imidazol-l-yl)-phenyl sulphone, H2OBA=4, 4'-oxybisbenzoic acid, H2PA=pamoic acid, BIDPT=4, 4'-bis(imidazol-l-yl)diphenyl thioether), have been hydrothermally synthesized and characterized by single X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. Compound 1 shows a two-fold 3D network with cds topology. Compound 2 is a 2D (4, 4) layer network and shows a 2D → 3D parallel-parallel polycatenation framework. Compound 3 exhibits an infinite chain, and such 1D chains are further interlinked into a 3D supramolecular structure via intermolecular and intramolecular hydrogen bonds. Compounds 1-3 could stably exist in aqueous solutions with pH=4-10. Compounds 1-3 demonstrated strong luminescence in aqueous solution, and fluorescence studies show that 1-3 could detect 2, 4, 6-trinitrophenol and Fe3+ with high sensitivity and selectivity by luminescent sensing.
Three Zn(Ⅱ)-based metal-organic frameworks with V-shaped ligands, namely {[Zn2(BIDPS)2(OBA)2]·DMA}n (1), {[Zn(BIDPT)(PA)]·DMF}n (2), and {[Zn(BIDPS)(PA)(H2O)2]·2H2O}n (3) (BIDPS =4, 4'-bis(imidazol-l-yl)-phenyl sulphone, H2OBA=4, 4'-oxybisbenzoic acid, H2PA=pamoic acid, BIDPT=4, 4'-bis(imidazol-l-yl)diphenyl thioether), have been hydrothermally synthesized and characterized by single X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. Compound 1 shows a two-fold 3D network with cds topology. Compound 2 is a 2D (4, 4) layer network and shows a 2D → 3D parallel-parallel polycatenation framework. Compound 3 exhibits an infinite chain, and such 1D chains are further interlinked into a 3D supramolecular structure via intermolecular and intramolecular hydrogen bonds. Compounds 1-3 could stably exist in aqueous solutions with pH=4-10. Compounds 1-3 demonstrated strong luminescence in aqueous solution, and fluorescence studies show that 1-3 could detect 2, 4, 6-trinitrophenol and Fe3+ with high sensitivity and selectivity by luminescent sensing.
2022, 38(12): 2491-2498
doi: 10.11862/CJIC.2022.239
Abstract:
A stable coordination polymer, [Cd2(L) (bpb) (H2O)4] ·0.5H4L (1) (H4L=1, 1'-ethylbiphenyl-3, 3', 5, 5'-tetracarboxylic acid, bpb=1, 4-di(pyridin-4-yl) benzene), were successfully constructed under solvothermal conditions. 1 exhibited excellent stability in different organic solvents and water. 1 could detect roxithromycin (ROX) and B4O72- in water by fluorescence quenching, and the detection limits were 0.21 and 1.59 μmol·L-1, respectively. 1 could be successfully used for the determination of ROX and B4O72- in Yanhe River water. Moreover, the possible sensing mechanisms are also discussed in detail.
A stable coordination polymer, [Cd2(L) (bpb) (H2O)4] ·0.5H4L (1) (H4L=1, 1'-ethylbiphenyl-3, 3', 5, 5'-tetracarboxylic acid, bpb=1, 4-di(pyridin-4-yl) benzene), were successfully constructed under solvothermal conditions. 1 exhibited excellent stability in different organic solvents and water. 1 could detect roxithromycin (ROX) and B4O72- in water by fluorescence quenching, and the detection limits were 0.21 and 1.59 μmol·L-1, respectively. 1 could be successfully used for the determination of ROX and B4O72- in Yanhe River water. Moreover, the possible sensing mechanisms are also discussed in detail.
2022, 38(12): 2499-2510
doi: 10.11862/CJIC.2022.241
Abstract:
Four new metal complexes, namely [Cu2(Cbiq)4(H2O)2]Br4·2H2O (1), [Zn(Cbiq)2(H2O)2]Br2·Cbiq·H2O (2), and [M3(Cbiq)8(μ-OH)2(H2O)2](ClO4)4·7H2O (M=Co (3), Mn (4)), were synthesized from the zwitterionic carboxylate ligand N-(4-carboxybenzyl)isoquinolinium bromide ((HCbiq)Br) with the corresponding metal salts. All these metal complexes were characterized by single crystal X-ray diffraction, elemental analyses, and IR. In complex 1, the centrosymmetric binuclear Cu(Ⅱ) are bridged by four Cbiq molecules and each Cu(Ⅱ) ion is further coordinated to one water molecule. In complex 2, the center Zn(Ⅱ) ion is coordinated to two unidentate Cbiq molecules and two water molecules. Complexes 3 and 4 have similar structures in which every two M(Ⅱ) ions are bridged by two Cbiq molecules and one hydroxo-O atom and the two peripheric M(Ⅱ) ions are further coordinated to two unidentate Cbiq molecules and one water molecule. Agarose gel electrophoresis (GE) studies on the cleavage of plasmid pBR322 DNA by complexes 1-4 indicated that complex 1 was capable of efficiently cleaving DNA under physiological conditions, most probably via an oxidative mechanism. Kinetic assay of complex 1 afforded the maximal catalytic rate constant kmax of 2.80 h-1 and Michaelis constant KM of 3.22 mmol·L-1. Ethidium bromide (EB) displacement experiments indicated that complex 1 exhibited high DNA binding affinity toward calf-thymus (CT) DNA. The docking method was used to predict the CT DNA binding affinity of complex 1, with the result that the binding free energy was -49.87 kJ·mol-1.
Four new metal complexes, namely [Cu2(Cbiq)4(H2O)2]Br4·2H2O (1), [Zn(Cbiq)2(H2O)2]Br2·Cbiq·H2O (2), and [M3(Cbiq)8(μ-OH)2(H2O)2](ClO4)4·7H2O (M=Co (3), Mn (4)), were synthesized from the zwitterionic carboxylate ligand N-(4-carboxybenzyl)isoquinolinium bromide ((HCbiq)Br) with the corresponding metal salts. All these metal complexes were characterized by single crystal X-ray diffraction, elemental analyses, and IR. In complex 1, the centrosymmetric binuclear Cu(Ⅱ) are bridged by four Cbiq molecules and each Cu(Ⅱ) ion is further coordinated to one water molecule. In complex 2, the center Zn(Ⅱ) ion is coordinated to two unidentate Cbiq molecules and two water molecules. Complexes 3 and 4 have similar structures in which every two M(Ⅱ) ions are bridged by two Cbiq molecules and one hydroxo-O atom and the two peripheric M(Ⅱ) ions are further coordinated to two unidentate Cbiq molecules and one water molecule. Agarose gel electrophoresis (GE) studies on the cleavage of plasmid pBR322 DNA by complexes 1-4 indicated that complex 1 was capable of efficiently cleaving DNA under physiological conditions, most probably via an oxidative mechanism. Kinetic assay of complex 1 afforded the maximal catalytic rate constant kmax of 2.80 h-1 and Michaelis constant KM of 3.22 mmol·L-1. Ethidium bromide (EB) displacement experiments indicated that complex 1 exhibited high DNA binding affinity toward calf-thymus (CT) DNA. The docking method was used to predict the CT DNA binding affinity of complex 1, with the result that the binding free energy was -49.87 kJ·mol-1.
2022, 38(12): 2511-2520
doi: 10.11862/CJIC.2022.246
Abstract:
Two transition-metal complexes, [Zn(suc)(HL)]n (1) and [Cd(suc)0.5(L)]n (2) (H2suc=succinic acid, HL=3-(2-pyridyl)pyrazole), have been achieved under hydrothermal conditions and structurally characterized by elemental analysis, IR spectrum, single-crystal X-ray diffraction, thermogravimetric analysis, fluorescent spectroscopy, and powder X-ray diffraction. In complex 1, the carboxyl ligand suc2- bridges the metal centers via bidentate and monodentate modes. The metal centers are coordinated by suc2- to form a 2D network structure. In 2, suc2- and L-ligands linked the Cd (Ⅱ) ions to form a 2D framework too. Besides, the quantum-chemical calculations were finished on 'molecular fragments'selected from the crystal structure of 1 and 2 by the PBE0/LANL2DZ method in the Gaussian16 program. The calculation results indicate the distinct covalent interaction between the coordinated atoms and Zn(Ⅱ) ion/Cd(Ⅱ) ion.
Two transition-metal complexes, [Zn(suc)(HL)]n (1) and [Cd(suc)0.5(L)]n (2) (H2suc=succinic acid, HL=3-(2-pyridyl)pyrazole), have been achieved under hydrothermal conditions and structurally characterized by elemental analysis, IR spectrum, single-crystal X-ray diffraction, thermogravimetric analysis, fluorescent spectroscopy, and powder X-ray diffraction. In complex 1, the carboxyl ligand suc2- bridges the metal centers via bidentate and monodentate modes. The metal centers are coordinated by suc2- to form a 2D network structure. In 2, suc2- and L-ligands linked the Cd (Ⅱ) ions to form a 2D framework too. Besides, the quantum-chemical calculations were finished on 'molecular fragments'selected from the crystal structure of 1 and 2 by the PBE0/LANL2DZ method in the Gaussian16 program. The calculation results indicate the distinct covalent interaction between the coordinated atoms and Zn(Ⅱ) ion/Cd(Ⅱ) ion.
2022, 38(12): 2521-2529
doi: 10.11862/CJIC.2022.245
Abstract:
Treatment of the parent complex [Fe2(CO)6(μ-SCH2CH(CH2CH3)S)] (1) with tri(2-furyl)phosphine, n-propyldiphenylphosphine, bis(diphenylphosphino)acetylene, or 1, 2-bis(diphenylphosphino)benzene and Me3NO ∙ 2H2O as the decarbonylating agent yielded the monosubstituted complexes [Fe2(CO)5(L)(μ-SCH2CH(CH2CH3)S)] (L=P(2-C4H3O)3, 2; Ph2PCH2CH2CH3, 3), bridging complex {[Fe2(CO)5(μ-SCH2CH(CH2CH3)S)]2(Ph2PC≡CPPh2)} (4), and chelating complex [Fe2(CO)4(κ2-(Ph2P)2(1, 2-C6H4))(μ-SCH2CH(CH2CH3)S)] (5), respectively. Complexes 2-5 have been characterized by elemental analysis, IR, and 1H (31P{1H}) NMR spectroscopy, as well as confirmed by single crystal X-ray diffraction analysis. Moreover, the electrochemistry of complexes 2-5 has been studied, showing that these complexes can catalyze the reduction of proton to H2 in the presence of a weak acid HOAc as a proton source.
Treatment of the parent complex [Fe2(CO)6(μ-SCH2CH(CH2CH3)S)] (1) with tri(2-furyl)phosphine, n-propyldiphenylphosphine, bis(diphenylphosphino)acetylene, or 1, 2-bis(diphenylphosphino)benzene and Me3NO ∙ 2H2O as the decarbonylating agent yielded the monosubstituted complexes [Fe2(CO)5(L)(μ-SCH2CH(CH2CH3)S)] (L=P(2-C4H3O)3, 2; Ph2PCH2CH2CH3, 3), bridging complex {[Fe2(CO)5(μ-SCH2CH(CH2CH3)S)]2(Ph2PC≡CPPh2)} (4), and chelating complex [Fe2(CO)4(κ2-(Ph2P)2(1, 2-C6H4))(μ-SCH2CH(CH2CH3)S)] (5), respectively. Complexes 2-5 have been characterized by elemental analysis, IR, and 1H (31P{1H}) NMR spectroscopy, as well as confirmed by single crystal X-ray diffraction analysis. Moreover, the electrochemistry of complexes 2-5 has been studied, showing that these complexes can catalyze the reduction of proton to H2 in the presence of a weak acid HOAc as a proton source.
2022, 38(12): 2530-2538
doi: 10.11862/CJIC.2022.248
Abstract:
In the presence of N ancillary ligands, imidazole (ImH) and 5-(4-pyridyl)tetrazole (4-PT), treatment of 3, 4-pyrazoledicarboxylic acid (H3pdc) with corresponding Mn(Ⅱ)/Zn(Ⅱ) metal salts afforded two complexes, [Mn(Hpdc) (ImH)(H2O)]n (1) and [Zn(Hpdc)(4-PT)(H2O)3]·2H2O (2). In the 1D coordination polymer 1 and mononuclear complex 2, the Hpdc2- ligand adopted μ2-κ∶O, N; κ∶O', O″ coordination mode and O, N-chelating mode, respectively, while the ImH and 4-PT ligands in 1 and 2 both acted as a monodentate ligand. In 1, in the influence of intermolecular N—H⋯O and O—H⋯O hydrogen bonds, the 1D coordination chains are packed into a 3D supramolecular structure. In 2, in the function of intermolecular O—H⋯O and O—H⋯N hydrogen bonds, the adjacent mononuclear components [Zn(Hpdc)(4-PT)(H2O)3] are packed into 2D structures, then these 2D layers and the lattice water molecules are interlinked and generated a 3D supramolecular architecture. Moreover, the luminescent properties of complexes 1 and 2 as well as the electrochemical property of 1 were also investigated.
In the presence of N ancillary ligands, imidazole (ImH) and 5-(4-pyridyl)tetrazole (4-PT), treatment of 3, 4-pyrazoledicarboxylic acid (H3pdc) with corresponding Mn(Ⅱ)/Zn(Ⅱ) metal salts afforded two complexes, [Mn(Hpdc) (ImH)(H2O)]n (1) and [Zn(Hpdc)(4-PT)(H2O)3]·2H2O (2). In the 1D coordination polymer 1 and mononuclear complex 2, the Hpdc2- ligand adopted μ2-κ∶O, N; κ∶O', O″ coordination mode and O, N-chelating mode, respectively, while the ImH and 4-PT ligands in 1 and 2 both acted as a monodentate ligand. In 1, in the influence of intermolecular N—H⋯O and O—H⋯O hydrogen bonds, the 1D coordination chains are packed into a 3D supramolecular structure. In 2, in the function of intermolecular O—H⋯O and O—H⋯N hydrogen bonds, the adjacent mononuclear components [Zn(Hpdc)(4-PT)(H2O)3] are packed into 2D structures, then these 2D layers and the lattice water molecules are interlinked and generated a 3D supramolecular architecture. Moreover, the luminescent properties of complexes 1 and 2 as well as the electrochemical property of 1 were also investigated.
2022, 38(12): 2539-2549
doi: 10.11862/CJIC.2022.253
Abstract:
Under hydrothermal conditions, a coordination polymer {[Cu2(Hdepa) (2, 2'-bpy)2(H2O)2]·2H2O}n was designed and synthesized based on ligands H5depa and 2, 2'-bpy (H5depa=2, 2', 3, 4', 5-diphenyl ether pentacarboxylic acid, 2, 2'-bpy=2, 2'-bipyridine). Its structure was characterized by elemental analysis, infrared spectroscopy, singlecrystal X-ray diffraction, and thermal stability analysis. The two central Cu2+ ions in coordination polymer 1 adopt a five-coordination with triangular bipyramid geometry. The incompletely deprotonated Hdepa4- ligand adopts a μ4-η1-η1-η1-η1 coordination mode. The 2D layers are connected by weak hydrogen bonds to form a 3D supramolecular structure. As a highly sensitive, selective, and multi-response fluorescent sensor, 1 could rapidly detect Fe3+ and p-nitrophenol (4-NP). In addition, the fluorescence quenching mechanism was also studied.
Under hydrothermal conditions, a coordination polymer {[Cu2(Hdepa) (2, 2'-bpy)2(H2O)2]·2H2O}n was designed and synthesized based on ligands H5depa and 2, 2'-bpy (H5depa=2, 2', 3, 4', 5-diphenyl ether pentacarboxylic acid, 2, 2'-bpy=2, 2'-bipyridine). Its structure was characterized by elemental analysis, infrared spectroscopy, singlecrystal X-ray diffraction, and thermal stability analysis. The two central Cu2+ ions in coordination polymer 1 adopt a five-coordination with triangular bipyramid geometry. The incompletely deprotonated Hdepa4- ligand adopts a μ4-η1-η1-η1-η1 coordination mode. The 2D layers are connected by weak hydrogen bonds to form a 3D supramolecular structure. As a highly sensitive, selective, and multi-response fluorescent sensor, 1 could rapidly detect Fe3+ and p-nitrophenol (4-NP). In addition, the fluorescence quenching mechanism was also studied.
2022, 38(12): 2550-2550
doi: 10.11862/CJIC.2022.275
Abstract:
