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2023 Volume 39 Issue 7
2023, 39(7): 1209-1222
doi: 10.11862/CJIC.2023.107
Abstract:
Due to their good durability and compatibility, calcium oxalate, hydroxyapatite, and calcium carbonate have been extensively studied as coating materials for the conservation of limestone relics in recent years. In this paper, the characteristics, preparation methods, and practical applications of the protective films composed of the above materials are reviewed. In terms of acid resistance of the materials, calcium oxalate is the best, then hydroxyapatite and calcium carbonate is number three. However, from the point of compatibility between limestone relics and protective materials, the law is the opposite. That is, calcium carbonate is the best, next comes hydroxyapatite, follows by calcium oxalate. Generally, inorganic calcium protective films can be prepared by both chemical and biological methods. Specifically, calcium oxalate and hydroxyapatite protective films can be obtained by the chemical reaction between limestones or their weathering crust and protectants such as oxalic acid, phosphoric acid, and their derivatives. The preparation conditions including the concentration, temperature, pH, and functional additives of the protectant are vital to the protective performance of the films. The calcium carbonate protective film, however, can be prepared by both chemical and biological methods. The former involves the carbonation reaction of all kinds of calcium precursors with carbon dioxide in the air. Carbon dioxide or carbonate ions, however, can be produced by bacteria or fungi, which can combine with calcium cations to form calcium carbonate deposition film. Calcium oxalate, hydroxyapatite, and calcium carbonate films began to be used in the surface protection of limestone relics around the world. Nevertheless, in practical operation, the preparation of the protective films with satisfying performance is still challenging, especially for the immovable stone relics with irregular shapes. So, greater efforts in the research of protective materials and technologies are still necessary in the future.
Due to their good durability and compatibility, calcium oxalate, hydroxyapatite, and calcium carbonate have been extensively studied as coating materials for the conservation of limestone relics in recent years. In this paper, the characteristics, preparation methods, and practical applications of the protective films composed of the above materials are reviewed. In terms of acid resistance of the materials, calcium oxalate is the best, then hydroxyapatite and calcium carbonate is number three. However, from the point of compatibility between limestone relics and protective materials, the law is the opposite. That is, calcium carbonate is the best, next comes hydroxyapatite, follows by calcium oxalate. Generally, inorganic calcium protective films can be prepared by both chemical and biological methods. Specifically, calcium oxalate and hydroxyapatite protective films can be obtained by the chemical reaction between limestones or their weathering crust and protectants such as oxalic acid, phosphoric acid, and their derivatives. The preparation conditions including the concentration, temperature, pH, and functional additives of the protectant are vital to the protective performance of the films. The calcium carbonate protective film, however, can be prepared by both chemical and biological methods. The former involves the carbonation reaction of all kinds of calcium precursors with carbon dioxide in the air. Carbon dioxide or carbonate ions, however, can be produced by bacteria or fungi, which can combine with calcium cations to form calcium carbonate deposition film. Calcium oxalate, hydroxyapatite, and calcium carbonate films began to be used in the surface protection of limestone relics around the world. Nevertheless, in practical operation, the preparation of the protective films with satisfying performance is still challenging, especially for the immovable stone relics with irregular shapes. So, greater efforts in the research of protective materials and technologies are still necessary in the future.
2023, 39(7): 1223-1234
doi: 10.11862/CJIC.2023.108
Abstract:
Porous organic polymer PTPA containing N, S heteroatoms has been prepared via oxidative coupling of thiophene. Then composite material Cu-Cu2O/PTPA was synthesized via solvothermal method and fully characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), N2 adsorption desorption, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). Under the mild conditions of 30 ℃ and open air, Cu-Cu2O/PTPA showed good catalytic activity towards selective oxidation of benzyl, allyl, and heterocyclic alcohols employing 2, 2, 6, 6-tetramethylpiperidine 1-oxyl (TEMPO) as a co-catalyst and N-methylimidazole (NMI) as an auxiliary ligand. Due to the high content of N and S heteroatoms in the material, Cu-Cu2O/PTPA showed excellent cycling stability for oxidation of benzyl alcohol, and the yield of product remained above 97% after 9 runs.
Porous organic polymer PTPA containing N, S heteroatoms has been prepared via oxidative coupling of thiophene. Then composite material Cu-Cu2O/PTPA was synthesized via solvothermal method and fully characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), N2 adsorption desorption, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM). Under the mild conditions of 30 ℃ and open air, Cu-Cu2O/PTPA showed good catalytic activity towards selective oxidation of benzyl, allyl, and heterocyclic alcohols employing 2, 2, 6, 6-tetramethylpiperidine 1-oxyl (TEMPO) as a co-catalyst and N-methylimidazole (NMI) as an auxiliary ligand. Due to the high content of N and S heteroatoms in the material, Cu-Cu2O/PTPA showed excellent cycling stability for oxidation of benzyl alcohol, and the yield of product remained above 97% after 9 runs.
2023, 39(7): 1235-1243
doi: 10.11862/CJIC.2023.116
Abstract:
One complex with formula [Tb(L)0.5(H2O)2]·7H2O (1) was prepared under the solvothermal condition by employing (1, 1′∶3′, 1″-triphenyl)-3, 3″, 4′, 5, 5″, 6′-hexacarboxylic acid (H6L) and Tb3+ ion. The structure and composition of complex 1 were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. The fluorescence property of complex 1 was also studied. The results show that complex 1 belongs to the orthorhombic system, Cmca space group with cell parameters: a=2.661 61(7) nm, b=1.421 03(4) nm, c=2.109 88(6) nm. Topological calculation shows that complex 1 is a novel (6, 6)-connected 3D network with the symbol (48.66.8)(49.66). Further study shows that complex 1 has strong fluorescence emission. It was sensitive in the detection of dimetridazole (MDZ) and tetracycline (TET) in an aqueous solution with high sensitivity, low detection limit, and good recyclability. The mechanism of fluorescence quenching was disclosed through the combination of experiments and density functional theory calculations.
One complex with formula [Tb(L)0.5(H2O)2]·7H2O (1) was prepared under the solvothermal condition by employing (1, 1′∶3′, 1″-triphenyl)-3, 3″, 4′, 5, 5″, 6′-hexacarboxylic acid (H6L) and Tb3+ ion. The structure and composition of complex 1 were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, infrared spectroscopy, elemental analysis, and thermogravimetric analysis. The fluorescence property of complex 1 was also studied. The results show that complex 1 belongs to the orthorhombic system, Cmca space group with cell parameters: a=2.661 61(7) nm, b=1.421 03(4) nm, c=2.109 88(6) nm. Topological calculation shows that complex 1 is a novel (6, 6)-connected 3D network with the symbol (48.66.8)(49.66). Further study shows that complex 1 has strong fluorescence emission. It was sensitive in the detection of dimetridazole (MDZ) and tetracycline (TET) in an aqueous solution with high sensitivity, low detection limit, and good recyclability. The mechanism of fluorescence quenching was disclosed through the combination of experiments and density functional theory calculations.
2023, 39(7): 1244-1252
doi: 10.11862/CJIC.2023.095
Abstract:
The ligands 1, 4-bis(2-(2-pyridyl)ethenyl)benzene (2-bpeb) and 1, 2-di(pyridin-4-yl)ethene (dpe) have been employed to react with terephthalic acid (H2PTA) and Co(NO3)2 under solvothermal conditions to fabricate two novel Co(Ⅱ)-MOFs (1 and 2). The structure of 1 manifests a 3D framework constituted by the Co-2-bpeb and Co-PTA chains, while complex 2 is a 3D framework constructed from the Co-PTA layers connected by the dpe ligand. Due to the existence of a large π-conjugated system in the pyridyl ligands and in consideration of the practical application, the fluorescence properties of 1 and 2 were investigated and the sensing experiments revealed that both of them could be used as a fluorescent sensor for detecting Fe3+ with good sensitivity and recyclability.
The ligands 1, 4-bis(2-(2-pyridyl)ethenyl)benzene (2-bpeb) and 1, 2-di(pyridin-4-yl)ethene (dpe) have been employed to react with terephthalic acid (H2PTA) and Co(NO3)2 under solvothermal conditions to fabricate two novel Co(Ⅱ)-MOFs (1 and 2). The structure of 1 manifests a 3D framework constituted by the Co-2-bpeb and Co-PTA chains, while complex 2 is a 3D framework constructed from the Co-PTA layers connected by the dpe ligand. Due to the existence of a large π-conjugated system in the pyridyl ligands and in consideration of the practical application, the fluorescence properties of 1 and 2 were investigated and the sensing experiments revealed that both of them could be used as a fluorescent sensor for detecting Fe3+ with good sensitivity and recyclability.
2023, 39(7): 1253-1260
doi: 10.11862/CJIC.2023.105
Abstract:
The precursor of PtCoMn alloy catalyst was synthesized with ethylene glycol as reducing agent under microwave heating. After high temperature heat treatment, the alloy was formed. Finally, the PtCoMn alloy catalyst was obtained by acid treatment. The composition, structure, and morphology of the catalyst were characterized by elemental analysis, X-ray diffraction, and transmission electron microscopy. The surface electronic structure and properties of the catalyst were studied by X-ray photoelectron spectroscopy and electrochemical workstation. The results showed that the activity and durability of the catalyst can be improved by the addition of proper amount of Mn. The mass specific activity (MA) of PtCoMn/C catalyst was 0.666 A·mgPt-1 at 0.9 V (vs RHE), which was 2.66 times that of conventional Pt/C and 1.30 times that of PtCo/C catalyst. In the 30 000-cycle catalyst accelerated durability test, electrochemical active area (ECSA) and MA of PtCoMn/C alloy catalyst only decreased by 6.9% and 27.1%, both of which were much lower than Pt/C catalyst.
The precursor of PtCoMn alloy catalyst was synthesized with ethylene glycol as reducing agent under microwave heating. After high temperature heat treatment, the alloy was formed. Finally, the PtCoMn alloy catalyst was obtained by acid treatment. The composition, structure, and morphology of the catalyst were characterized by elemental analysis, X-ray diffraction, and transmission electron microscopy. The surface electronic structure and properties of the catalyst were studied by X-ray photoelectron spectroscopy and electrochemical workstation. The results showed that the activity and durability of the catalyst can be improved by the addition of proper amount of Mn. The mass specific activity (MA) of PtCoMn/C catalyst was 0.666 A·mgPt-1 at 0.9 V (vs RHE), which was 2.66 times that of conventional Pt/C and 1.30 times that of PtCo/C catalyst. In the 30 000-cycle catalyst accelerated durability test, electrochemical active area (ECSA) and MA of PtCoMn/C alloy catalyst only decreased by 6.9% and 27.1%, both of which were much lower than Pt/C catalyst.
2023, 39(7): 1261-1274
doi: 10.11862/CJIC.2023.100
Abstract:
In this work, we proposed a novel strategy, doping single atom Ge promoter to the Cu(111) surface, to overcome the shortcomings such as the difficulties in the adsorption and activation of CO2 molecules and the complex by-products produced in both the reverse water gas shift (RWGS) and the formate reaction pathway. The electron modulating effect of single atom Ge species on the reaction mechanism of CO2 hydrogenation to methanol over Ge-Cu(111) surface was detailly investigated by the density functional theory (DFT) method. The results show that the electron supply ability of Cu atoms adjacent to the single Ge atom is greatly enhanced due to the electron modulating effect of Ge species, which leads to the improved interaction between the CO2 molecule and the active interface: the adsorption energy of CO2 over the single atom Ge promoted Cu(111) surface was approximately 1.5 times that over the pure Cu(111) surface and approximately 2.4 times that over clustered Pd modified Cu(111) surface, respectively. The enhanced CO2 adsorption ability further resulted in a decline in the activation energy of the reaction rate control step for the RWGS pathway by about 20 kJ·mol-1, meanwhile, there emerged three new potential RWGS reaction routes that only produced methanol. Moreover, the formate reaction pathway is kinetically inhibited over the Ge-Cu(111) surface, leading to the reduced by-products such as CO and hydrocarbons to improve both the selectivity of methanol in the CO2 hydrogenation to methanol reaction.
In this work, we proposed a novel strategy, doping single atom Ge promoter to the Cu(111) surface, to overcome the shortcomings such as the difficulties in the adsorption and activation of CO2 molecules and the complex by-products produced in both the reverse water gas shift (RWGS) and the formate reaction pathway. The electron modulating effect of single atom Ge species on the reaction mechanism of CO2 hydrogenation to methanol over Ge-Cu(111) surface was detailly investigated by the density functional theory (DFT) method. The results show that the electron supply ability of Cu atoms adjacent to the single Ge atom is greatly enhanced due to the electron modulating effect of Ge species, which leads to the improved interaction between the CO2 molecule and the active interface: the adsorption energy of CO2 over the single atom Ge promoted Cu(111) surface was approximately 1.5 times that over the pure Cu(111) surface and approximately 2.4 times that over clustered Pd modified Cu(111) surface, respectively. The enhanced CO2 adsorption ability further resulted in a decline in the activation energy of the reaction rate control step for the RWGS pathway by about 20 kJ·mol-1, meanwhile, there emerged three new potential RWGS reaction routes that only produced methanol. Moreover, the formate reaction pathway is kinetically inhibited over the Ge-Cu(111) surface, leading to the reduced by-products such as CO and hydrocarbons to improve both the selectivity of methanol in the CO2 hydrogenation to methanol reaction.
2023, 39(7): 1275-1286
doi: 10.11862/CJIC.2023.097
Abstract:
Herein, a quasi-parallel CoFe layer double hydroxide (CoFe LDH) nanosheet array was employed as precursor to regulate the deposition of MoO2 nanoparticles with abundant oxygen vacancies array by in-situ loading and calcination process. The as-obtained CoFeOx/MoO2 nanoarray electrode showed the enhanced hydrogen evolution reaction (HER) activity, while it delivered the current densities of 10 and 1 000 mA·cm-2 at overpotential of 40 and 217 mV, respectively. Besides, the current density of 50 mA·cm-2 for CoFeOx/MoO2 electrode was maintained at an overpotential of 100 mV up to 125 h of operation.
Herein, a quasi-parallel CoFe layer double hydroxide (CoFe LDH) nanosheet array was employed as precursor to regulate the deposition of MoO2 nanoparticles with abundant oxygen vacancies array by in-situ loading and calcination process. The as-obtained CoFeOx/MoO2 nanoarray electrode showed the enhanced hydrogen evolution reaction (HER) activity, while it delivered the current densities of 10 and 1 000 mA·cm-2 at overpotential of 40 and 217 mV, respectively. Besides, the current density of 50 mA·cm-2 for CoFeOx/MoO2 electrode was maintained at an overpotential of 100 mV up to 125 h of operation.
2023, 39(7): 1287-1294
doi: 10.11862/CJIC.2023.092
Abstract:
Three organotin 9-fluorenone-4-carboxylate compounds, triphenyltin 9‑fluorenone‑4‑carboxylate [(C6H5)3Sn(C14H7O3)] (1), tricyclohexyltin 9-fluorenone-4-carboxylate [(C6H11)3Sn(C14H7O3)] (2), and tri(2-methyl-2-phenylpropyl) tin 9-fluorenone-4-carboxylate [(C6H5C(CH3)2CH2)3Sn(C14H7O3)] (3), were synthesized by the solvothermal method using methanol as a solvent. The compounds were characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C, and 119Sn), and thermogravimetric analysis. The crystal structures of the compounds were determined by single-crystal X-ray diffraction. The compounds were studied by quantum chemical calculation and in vitro anticancer activity. The results show that compound 1 has a 1D chain structure and the central tin atom is a five-coordinated distorted trigonal bipyramid configuration; compounds 2 and 3 are single tin nuclear molecules and the tin atoms are four-coordinated distorted tetrahedron configurations. The compounds have good inhibitory activity on the human cervical carcinoma cell line (HeLa), human liver cancer cell line (HUH-7), human non-small cell lung cancer cell line (A549), human lung adenocarcinoma cell line (H1975) and breast cancer cell line (MCF-7).
Three organotin 9-fluorenone-4-carboxylate compounds, triphenyltin 9‑fluorenone‑4‑carboxylate [(C6H5)3Sn(C14H7O3)] (1), tricyclohexyltin 9-fluorenone-4-carboxylate [(C6H11)3Sn(C14H7O3)] (2), and tri(2-methyl-2-phenylpropyl) tin 9-fluorenone-4-carboxylate [(C6H5C(CH3)2CH2)3Sn(C14H7O3)] (3), were synthesized by the solvothermal method using methanol as a solvent. The compounds were characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C, and 119Sn), and thermogravimetric analysis. The crystal structures of the compounds were determined by single-crystal X-ray diffraction. The compounds were studied by quantum chemical calculation and in vitro anticancer activity. The results show that compound 1 has a 1D chain structure and the central tin atom is a five-coordinated distorted trigonal bipyramid configuration; compounds 2 and 3 are single tin nuclear molecules and the tin atoms are four-coordinated distorted tetrahedron configurations. The compounds have good inhibitory activity on the human cervical carcinoma cell line (HeLa), human liver cancer cell line (HUH-7), human non-small cell lung cancer cell line (A549), human lung adenocarcinoma cell line (H1975) and breast cancer cell line (MCF-7).
2023, 39(7): 1295-1302
doi: 10.11862/CJIC.2023.110
Abstract:
A Schiff base probe, namely N′ -(quinoxaline-2-ylmethylene) pyridinyl hydrazide (1) was produced by a simple condensation reaction and was fully characterized through 1H NMR, 13C NMR, and ESI-MS. Probe 1 was nonemissive while displaying a strong emission at 500 nm in the presence of Zn2+. This fluorescence enhancement was highly selective and sensitive toward Zn2+ over other common cations, with a detection limit of 0.16 μmol·L-1. The coordination mode of 1 with Zn2+ was proposed by means of ESI-MS, 1H NMR, and UV-Vis. The crystal structure of the 1-Zn2+ complex was characterized by X- ray single- crystal diffraction, further confirming the coordination behavior of the probe. The results showed that the probe can coordinate two independent Zn2+ ions via ONN and NN donor sets, which are connected by bridged CH3O- and Cl- to form a 1D chain. Finally, the probe was used to trace Zn2+ in HeLa cells.
A Schiff base probe, namely N′ -(quinoxaline-2-ylmethylene) pyridinyl hydrazide (1) was produced by a simple condensation reaction and was fully characterized through 1H NMR, 13C NMR, and ESI-MS. Probe 1 was nonemissive while displaying a strong emission at 500 nm in the presence of Zn2+. This fluorescence enhancement was highly selective and sensitive toward Zn2+ over other common cations, with a detection limit of 0.16 μmol·L-1. The coordination mode of 1 with Zn2+ was proposed by means of ESI-MS, 1H NMR, and UV-Vis. The crystal structure of the 1-Zn2+ complex was characterized by X- ray single- crystal diffraction, further confirming the coordination behavior of the probe. The results showed that the probe can coordinate two independent Zn2+ ions via ONN and NN donor sets, which are connected by bridged CH3O- and Cl- to form a 1D chain. Finally, the probe was used to trace Zn2+ in HeLa cells.
2023, 39(7): 1303-1314
doi: 10.11862/CJIC.2023.104
Abstract:
In this work, the overall formation of gel groups was studied by using the synthesized 4, 4, 4-tricarboxytri-phenylamine (H3TCA) as the main ligand. A supramolecular amorphous zirconium - based organometallic gel (Zr-MOG) was synthesized by the solvothermal method. Amorphous Zr-MOG was synthesized by gelation of UIO -66 (i.e. Zr- MOF) by a simple method of constant time- controlled crystallization. The gelation of precursor ZrCl4 was promoted by changing the ratio of metal ligands. The precursor ZrCl4 forms oxide and hydroxide bridges at room temperature, which promotes the formation of [Zr6O4(OH)4]12+ clusters and induces rapid and excessive nucleation rates. The results showed that the prepared Zr-MOG had the multi-layer structure of gel soft materials and amorphous polymer network, and had good adsorption capacity for Pb(Ⅱ). A series of studies on its adsorption properties were made to verify its recyclability and reusability. In addition, the transformation between crystalline MOF and highly dispersed amorphous MOG was successfully realized by using glacial acetic acid as a crystallization accelerator.
In this work, the overall formation of gel groups was studied by using the synthesized 4, 4, 4-tricarboxytri-phenylamine (H3TCA) as the main ligand. A supramolecular amorphous zirconium - based organometallic gel (Zr-MOG) was synthesized by the solvothermal method. Amorphous Zr-MOG was synthesized by gelation of UIO -66 (i.e. Zr- MOF) by a simple method of constant time- controlled crystallization. The gelation of precursor ZrCl4 was promoted by changing the ratio of metal ligands. The precursor ZrCl4 forms oxide and hydroxide bridges at room temperature, which promotes the formation of [Zr6O4(OH)4]12+ clusters and induces rapid and excessive nucleation rates. The results showed that the prepared Zr-MOG had the multi-layer structure of gel soft materials and amorphous polymer network, and had good adsorption capacity for Pb(Ⅱ). A series of studies on its adsorption properties were made to verify its recyclability and reusability. In addition, the transformation between crystalline MOF and highly dispersed amorphous MOG was successfully realized by using glacial acetic acid as a crystallization accelerator.
2023, 39(7): 1315-1324
doi: 10.11862/CJIC.2023.091
Abstract:
An efficient heterogeneous catalyst ZIF-67/CeO2 composites were synthesized by a precipitation method, and developed for the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol. The physicochemical properties of the ZIF-67/CeO2 catalysts were investigated by X-ray diffraction, N2 adsorption - desorption, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The results demonstrated that the introduction of ZIF-67 causes more oxygen vacancies to be generated onto CeO2. Among the ZIF-67/CeO2 catalysts, 0.3-ZIF-67/CeO2 (0.3 was the molar ratio of Co and Ce) showed the best catalytic performance due to its high specific surface area, mesoporous structure, and high CO2 adsorption capacity. Yield of 3.79 mmolDMC·gcat-1 was achieved at a temperature of 140 ℃ and a pressure of 4.5 MPa for 4 h.
An efficient heterogeneous catalyst ZIF-67/CeO2 composites were synthesized by a precipitation method, and developed for the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol. The physicochemical properties of the ZIF-67/CeO2 catalysts were investigated by X-ray diffraction, N2 adsorption - desorption, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The results demonstrated that the introduction of ZIF-67 causes more oxygen vacancies to be generated onto CeO2. Among the ZIF-67/CeO2 catalysts, 0.3-ZIF-67/CeO2 (0.3 was the molar ratio of Co and Ce) showed the best catalytic performance due to its high specific surface area, mesoporous structure, and high CO2 adsorption capacity. Yield of 3.79 mmolDMC·gcat-1 was achieved at a temperature of 140 ℃ and a pressure of 4.5 MPa for 4 h.
2023, 39(7): 1325-1337
doi: 10.11862/CJIC.2023.102
Abstract:
The development of low-cost, high-efficiency, and robust electrocatalysts with non-precious metal is the key to realizing large-scale hydrogen production by water electrolysis. Herein, a highly amorphous Co1Fe1-P film composed of ultrathin two-dimensional nanosheets was successfully loaded onto the nickel foam via a facile and reasonable electrodeposition method. Owing to the unique morphology, low-energy barrier provided by highly amorphous structure, optimized electronic structure, and strong synergistic effects of cobalt phosphides and iron phosphides, the as-fabricated Co1Fe1-P/NF electrode exhibited outstanding electrocatalytic performance for oxygen evolution reaction (OER) with the low overpotentials of 274.4 and 329.5 mV at 10 and 100 mA·cm-2 in 1.0 mol·L-1 KOH, respectively. The corresponding Tafel slope was 45.3 mV·dec-1, comparing favorably to that of commercial RuO2 catalyst. Notably, the 100-hour chronopotentiometry at 10 mA·cm-2 and 1 000-cycle voltammetry tests for OER with negligible attenuation confirmed the excellent stability and durability of Co1Fe1-P/NF.
The development of low-cost, high-efficiency, and robust electrocatalysts with non-precious metal is the key to realizing large-scale hydrogen production by water electrolysis. Herein, a highly amorphous Co1Fe1-P film composed of ultrathin two-dimensional nanosheets was successfully loaded onto the nickel foam via a facile and reasonable electrodeposition method. Owing to the unique morphology, low-energy barrier provided by highly amorphous structure, optimized electronic structure, and strong synergistic effects of cobalt phosphides and iron phosphides, the as-fabricated Co1Fe1-P/NF electrode exhibited outstanding electrocatalytic performance for oxygen evolution reaction (OER) with the low overpotentials of 274.4 and 329.5 mV at 10 and 100 mA·cm-2 in 1.0 mol·L-1 KOH, respectively. The corresponding Tafel slope was 45.3 mV·dec-1, comparing favorably to that of commercial RuO2 catalyst. Notably, the 100-hour chronopotentiometry at 10 mA·cm-2 and 1 000-cycle voltammetry tests for OER with negligible attenuation confirmed the excellent stability and durability of Co1Fe1-P/NF.
2023, 39(7): 1338-1348
doi: 10.11862/CJIC.2023.106
Abstract:
A simple, quick, and efficient chemical oxidation technique was employed to fabricate excellent biocompatible orange fluorescence graphene oxide quantum dots (GOQDs) with affordable, widely available graphite flake as the raw material. The as-prepared GOQDs have uniform sizes of ca. 7.2 nm, highly crystallized core with a lattice spacing of 0.20 nm, and oxidized peripherals. Unlike most reported doped-carbon dots, the GOQDs displayed orange-red independent fluorescent emission when the excitation wavelength was changed. The pH dependence emission, strong resistance of photobleaching, low cytotoxicity, good water solubility (ρ=10 mg·mL-1), and excellent biocompatibility behaviors made GOQDs successfully applied to live cell pH fluctuation imaging.
A simple, quick, and efficient chemical oxidation technique was employed to fabricate excellent biocompatible orange fluorescence graphene oxide quantum dots (GOQDs) with affordable, widely available graphite flake as the raw material. The as-prepared GOQDs have uniform sizes of ca. 7.2 nm, highly crystallized core with a lattice spacing of 0.20 nm, and oxidized peripherals. Unlike most reported doped-carbon dots, the GOQDs displayed orange-red independent fluorescent emission when the excitation wavelength was changed. The pH dependence emission, strong resistance of photobleaching, low cytotoxicity, good water solubility (ρ=10 mg·mL-1), and excellent biocompatibility behaviors made GOQDs successfully applied to live cell pH fluctuation imaging.
2023, 39(7): 1349-1359
doi: 10.11862/CJIC.2023.086
Abstract:
One of the effective approaches to obtaining functional carbon materials is selecting some appropriate biomass materials. In this work, the high nitrogen-doped porous carbon nanofibers (NPCF) can be obtained by one-step pyrolysis of potassium citrate and melamine. The NPCF electrode delivered capacities of 218 and 140 mAh·g-1 at current densities of 0.1 and 1.0 A·g-1, respectively. Concurrently, the sodium ion capacitors (SICs) with NPCF anode show outstanding rate performance and long lifespan for over 2 500 cycles at 1.0 A·g-1.
One of the effective approaches to obtaining functional carbon materials is selecting some appropriate biomass materials. In this work, the high nitrogen-doped porous carbon nanofibers (NPCF) can be obtained by one-step pyrolysis of potassium citrate and melamine. The NPCF electrode delivered capacities of 218 and 140 mAh·g-1 at current densities of 0.1 and 1.0 A·g-1, respectively. Concurrently, the sodium ion capacitors (SICs) with NPCF anode show outstanding rate performance and long lifespan for over 2 500 cycles at 1.0 A·g-1.
2023, 39(7): 1360-1368
doi: 10.11862/CJIC.2023.111
Abstract:
Two isomorphous mononuclear complexes [M(tpc)3(H2O)3]·H2O, where M=Dy (1), Tm (2), were synthesized through the reaction of 5-(trifluoromethyl) pyridine-2-carboxylic acid (Htpc), DyCl3·6H2O, and TmCl3·3H2O. The crystallographic details of complexes 1 and 2 reveal a monoclinic crystal system with the P21/c space group. Metal ions in the two complexes are eight-coordinated and located in the slightly deformed dodecahedron geometry. The fluorescence data reveal that complexes 1 and 2 could interact with bovine serum albumin (BSA) through the static quenching mechanism with the quenching constant Ksv ranging from 105 to 106 L·mol-1. Hydrophobic interaction plays an important role in the interaction of complexes and BSA since both ΔH and ΔS values are positive. The binding constant between the two complexes and BSA was about 104 L·mol-1 at 25 ℃, which indicates the complexes and BSA have moderate interactions.
Two isomorphous mononuclear complexes [M(tpc)3(H2O)3]·H2O, where M=Dy (1), Tm (2), were synthesized through the reaction of 5-(trifluoromethyl) pyridine-2-carboxylic acid (Htpc), DyCl3·6H2O, and TmCl3·3H2O. The crystallographic details of complexes 1 and 2 reveal a monoclinic crystal system with the P21/c space group. Metal ions in the two complexes are eight-coordinated and located in the slightly deformed dodecahedron geometry. The fluorescence data reveal that complexes 1 and 2 could interact with bovine serum albumin (BSA) through the static quenching mechanism with the quenching constant Ksv ranging from 105 to 106 L·mol-1. Hydrophobic interaction plays an important role in the interaction of complexes and BSA since both ΔH and ΔS values are positive. The binding constant between the two complexes and BSA was about 104 L·mol-1 at 25 ℃, which indicates the complexes and BSA have moderate interactions.
2023, 39(7): 1369-1378
doi: 10.11862/CJIC.2023.112
Abstract:
The development of metal chalcogenide non-supertetrahedral (non-Tn) cluster materials composed of metal In and Sn is very important for realizing the structural diversity of the materials and enriching their photoelectric applications. Herein, a series of new non-Tn cluster-based compounds C7H13N2[InS2] (1), (C7H13N2)4[In2S11Sn3] (2), and (C7H13N2)3[In3S12Sn3] (3) were prepared by the solvothermal method, where C7H13N2=protonated 1, 5-diazabicyclo[4.3.0]non-5-ene. The three compounds are formed by the combination of {SnS4}, {InS4}, or {InS5} coordination units in the way of edge-sharing or vertex-sharing. The electrocatalytic oxygen reduction reaction (ORR) study showed that the reduction peak potentials of compounds 1-3 were 0.6, 0.64, and 0.65 V, respectively, which indicates that compounds 2 and 3 containing Sn(Ⅳ) have better catalytic performance. More than that, the Koutecky-Levich plot analysis showed that the composition ratio of In and Sn in the compounds has a significant modulating effect on the ORR catalytic pathways.
The development of metal chalcogenide non-supertetrahedral (non-Tn) cluster materials composed of metal In and Sn is very important for realizing the structural diversity of the materials and enriching their photoelectric applications. Herein, a series of new non-Tn cluster-based compounds C7H13N2[InS2] (1), (C7H13N2)4[In2S11Sn3] (2), and (C7H13N2)3[In3S12Sn3] (3) were prepared by the solvothermal method, where C7H13N2=protonated 1, 5-diazabicyclo[4.3.0]non-5-ene. The three compounds are formed by the combination of {SnS4}, {InS4}, or {InS5} coordination units in the way of edge-sharing or vertex-sharing. The electrocatalytic oxygen reduction reaction (ORR) study showed that the reduction peak potentials of compounds 1-3 were 0.6, 0.64, and 0.65 V, respectively, which indicates that compounds 2 and 3 containing Sn(Ⅳ) have better catalytic performance. More than that, the Koutecky-Levich plot analysis showed that the composition ratio of In and Sn in the compounds has a significant modulating effect on the ORR catalytic pathways.
2023, 39(7): 1379-1388
doi: 10.11862/CJIC.2023.101
Abstract:
A zinc coordination polymer (Zn-CP) based on H4dpa and bpy ligands (H4dpa=4-(2, 4-dicarboxylic phenoxyl) phthalic acid, bpy=4, 4′-dipyridine), namely [Zn(H2dpa)(bpy)1.5]n (1), has been hydrothermal synthesized and structurally characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction analysis. 1 shows 1D double chain based on Zn2+ ion, H2dpa2- and bpy ligand. The adjacent 1D double chains further expand into a 3D supramolecular network through hydrogen bonding. Fluorescence studies show that 1 is a fluorescence sensor with high sensitivity, good selectivity, and multiple responses, which can be used for the detection of pesticides and nitro explosives. Interestingly, 2, 4, 6-trinitrobenzene (TNP), and pyrimethanil (Pth) had an obvious quenching effect on the fluorescence emission of 1, while imazalil (Ima) had an enhancement effect on the fluorescence of 1. In addition, the fluorescence mechanism was investigated by means of UV-Vis absorption spectrum, fluorescence lifetime, and X-ray photoelectron spectroscopy.
A zinc coordination polymer (Zn-CP) based on H4dpa and bpy ligands (H4dpa=4-(2, 4-dicarboxylic phenoxyl) phthalic acid, bpy=4, 4′-dipyridine), namely [Zn(H2dpa)(bpy)1.5]n (1), has been hydrothermal synthesized and structurally characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction analysis. 1 shows 1D double chain based on Zn2+ ion, H2dpa2- and bpy ligand. The adjacent 1D double chains further expand into a 3D supramolecular network through hydrogen bonding. Fluorescence studies show that 1 is a fluorescence sensor with high sensitivity, good selectivity, and multiple responses, which can be used for the detection of pesticides and nitro explosives. Interestingly, 2, 4, 6-trinitrobenzene (TNP), and pyrimethanil (Pth) had an obvious quenching effect on the fluorescence emission of 1, while imazalil (Ima) had an enhancement effect on the fluorescence of 1. In addition, the fluorescence mechanism was investigated by means of UV-Vis absorption spectrum, fluorescence lifetime, and X-ray photoelectron spectroscopy.
2023, 39(7): 1389-1406
doi: 10.11862/CJIC.2023.109
Abstract:
A novel Zn(Ⅱ) metal-organic framework (MOF) [Zn2(Hdepa)(dya)2]n (1) (H5depa=2, 2′, 3, 4′, 5-diphenyl ether pentacarboxylic, dya=2, 2′-dipyridyl amine) was successfully prepared. Single-crystal X-ray diffraction analysis indicates that MOF 1 is composed of two Zn2+ ions joining one Hdepa4- ion and two dya molecules, forming a 3D framework through hydrogen bonding. The phase purity of the MOF 1 was demonstrated by powder X-ray diffraction and IR. Interestingly, 1 has excellent fluorescence properties and thermal stability. Notably, due to its excellent fluorescence performance, the high sensitivity and selectivity of 1 enable it to be used as a fluorescence sensor to detect C6H5CHO (BZH), tetracycline (TC), 2, 4, 6-trinitrophenol (TNP), fluazinam (Flu), Cr2O72-, and Fe3+. In addition, the quenching process of Fe3+, TC, and BZH to MOF 1 was analyzed by fluorescence lifetime, and the fluorescence quenching mechanism of Fe3+, Cr2O72-, TNP, TC, BZH, and Flu was studied by energy transfer.
A novel Zn(Ⅱ) metal-organic framework (MOF) [Zn2(Hdepa)(dya)2]n (1) (H5depa=2, 2′, 3, 4′, 5-diphenyl ether pentacarboxylic, dya=2, 2′-dipyridyl amine) was successfully prepared. Single-crystal X-ray diffraction analysis indicates that MOF 1 is composed of two Zn2+ ions joining one Hdepa4- ion and two dya molecules, forming a 3D framework through hydrogen bonding. The phase purity of the MOF 1 was demonstrated by powder X-ray diffraction and IR. Interestingly, 1 has excellent fluorescence properties and thermal stability. Notably, due to its excellent fluorescence performance, the high sensitivity and selectivity of 1 enable it to be used as a fluorescence sensor to detect C6H5CHO (BZH), tetracycline (TC), 2, 4, 6-trinitrophenol (TNP), fluazinam (Flu), Cr2O72-, and Fe3+. In addition, the quenching process of Fe3+, TC, and BZH to MOF 1 was analyzed by fluorescence lifetime, and the fluorescence quenching mechanism of Fe3+, Cr2O72-, TNP, TC, BZH, and Flu was studied by energy transfer.
2023, 39(7): 1407-1414
doi: 10.11862/CJIC.2023.089
Abstract:
Metal-organic frameworks (MOFs) with uniform porosity and large surface areas can function as carriers of immobilized enzymes. However, drawbacks including long response times or enzyme leakage have hindered their applicability. In this study, we selected a peroxidase-like MIL-101 as a carrier, glutaraldehyde (GA) as a cross-linking agent, and glucose oxidase (GOx) was immobilized on the carrier by cross-linking method, and a simulated multi-enzyme system GOx@GA@MIL-101was established. The as-prepared composite can further efficiently catalyze the cascade reaction to detect glucose. GOx@GA@MIL-101 had a faster catalytic discoloration effect (30 s).
Metal-organic frameworks (MOFs) with uniform porosity and large surface areas can function as carriers of immobilized enzymes. However, drawbacks including long response times or enzyme leakage have hindered their applicability. In this study, we selected a peroxidase-like MIL-101 as a carrier, glutaraldehyde (GA) as a cross-linking agent, and glucose oxidase (GOx) was immobilized on the carrier by cross-linking method, and a simulated multi-enzyme system GOx@GA@MIL-101was established. The as-prepared composite can further efficiently catalyze the cascade reaction to detect glucose. GOx@GA@MIL-101 had a faster catalytic discoloration effect (30 s).
2023, 39(7): 1415-1428
doi: 10.11862/CJIC.2023.096
Abstract:
Herein, MIL-101(Fe)@BiOI composites have been synthesized by hydrothermal method and then calcined to get BiFeO3@Fe2O3@BiOI composites with high photocatalytic capacity. The composition, structure, and morphology of the composites were characterized by X-ray diffraction, scanning electron microscopy, and UV-Vis diffuse reflection absorption spectroscopy. The effects of composite ratio (mass ratio), pH, and concentration on photocatalytic performance were studied. Electrochemical impedance spectroscopy, photocurrent response, and Mott-Schottky curve test and analysis show that BiFeO3@Fe2O3@BiOI shows stronger photocurrent response and lower charge transfer resistance. The degradation activity of BiFeO3@Fe2O3@BiOI showed the highest in neutral conditions with a removal efficiency of 81% when the mass ratio was 1∶1∶1.
Herein, MIL-101(Fe)@BiOI composites have been synthesized by hydrothermal method and then calcined to get BiFeO3@Fe2O3@BiOI composites with high photocatalytic capacity. The composition, structure, and morphology of the composites were characterized by X-ray diffraction, scanning electron microscopy, and UV-Vis diffuse reflection absorption spectroscopy. The effects of composite ratio (mass ratio), pH, and concentration on photocatalytic performance were studied. Electrochemical impedance spectroscopy, photocurrent response, and Mott-Schottky curve test and analysis show that BiFeO3@Fe2O3@BiOI shows stronger photocurrent response and lower charge transfer resistance. The degradation activity of BiFeO3@Fe2O3@BiOI showed the highest in neutral conditions with a removal efficiency of 81% when the mass ratio was 1∶1∶1.
2023, 39(7): 1429-1439
doi: 10.11862/CJIC.2023.090
Abstract:
This paper constructed an all-nanowire photocatalytic fuel cell with enhanced mass and electron transfer by integrating TiO2 nanowire array photoanodes on three-dimensional (3D) hierarchical carbon cloth and platinized Si nanowire array photocathodes. Under light illumination, the potholes generated at the microfluidic photoanodes effectively oxidize various harmful contaminants, which significantly enhanced the reduction of water by photoelectrons for hydrogen gas production. Compared with conventional planar photoelectrodes, the all-nanowire photocatalytic fuel cell can efficiently degrade simulated dye wastewater and simultaneously generate hydrogen new energy without requiring an external bias voltage.
This paper constructed an all-nanowire photocatalytic fuel cell with enhanced mass and electron transfer by integrating TiO2 nanowire array photoanodes on three-dimensional (3D) hierarchical carbon cloth and platinized Si nanowire array photocathodes. Under light illumination, the potholes generated at the microfluidic photoanodes effectively oxidize various harmful contaminants, which significantly enhanced the reduction of water by photoelectrons for hydrogen gas production. Compared with conventional planar photoelectrodes, the all-nanowire photocatalytic fuel cell can efficiently degrade simulated dye wastewater and simultaneously generate hydrogen new energy without requiring an external bias voltage.
