Table of Content

10 March 2024, Volume 45 Issue 3

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Cover and Content of Chemical Journal of Chinese Universities Vol.45 No.3(2024)

2024, 45(3):  1. 

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Review

Research Progress of Electrocatalytic Ammonia Synthesis from Different Nitrogen Sources

ZHAO Xiaoguang, WANG Yunlong, YIN Haibo, QU Yakun, SU Haiwei, FANG Wei

2024, 45(3):  20230527.  doi:10.7503/cjcu20230527

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Ammonia is an important raw material for fertilizer production and chemical industry， and is also a good carbon-free energy storage fuel. Compared with the Haber-Bosch method for industrial-scale ammonia synthesis with high energy consumption and low conversion rate， the electrocatalytic ammonia synthesis method has the advantages of green and high efficiency under mild environmental conditions. This article reviews the reaction mechanism of electrocatalytic ammonia synthesis when using nitrogen， nitrate， and nitrogen oxide as different nitrogen sources. Based on the characteristics of different nitrogen sources， the research progress and advantages of each are analyzed. The problems of difficulty in controlling intermediates and reaction paths for nitrate reduction because of the large elemental valence span， complexity of the nitrogen oxide system， difficulty in controlling the hydrogen evolution reaction， and difficulty in dissolving nitrogen in water for activation are discussed， respectively. The solutions are summarized to develop high activity catalysts with different strategies to improve the reaction efficiency and selectivity， to optimize the reaction device to reduce the influence of mass transfer， and to select different electrolyte systems to improve the reaction process.



Article: Inorganic Chemistry

Storage Weathering Resistance of Zeolitic Acoustically Enhanced Materials

MENG Qinghua, SHI Chao

2024, 45(3):  20230474.  doi:10.7503/cjcu20230474

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In this work， the effects of different humidity and organic compounds on resonance frequency offsets（RFOs） of acoustically enhanced materials（AEM） were studied. Undergoing 25 ℃/50% relative humidity（RH） or 25 ℃/95%RH storage， coexisting with organic compounds， the changes of RFOs of AEM， composed of zeolite with various silicon-aluminum ratios（SAR）， were comprehensively discussed. The results showed that for the AEM composed of zeolite with a specialized silicon-aluminum ratio， the RFOs did not change significantly， after 25 ℃/50%RH and 25 ℃/95%RH storage. The results of the nitrogen adsorption experiment at 25 ℃/50%RH and 25 ℃/95%RH showed that nitrogen molecules occupied only a small part of the specific surface area at 25 ℃， and the presence of water molecules did not affect the adsorption of nitrogen molecules. The water molecules adsorbed at 25 ℃/95%RH will gradually desorb after standing at 25 ℃/50%RH. After coexisting with different types of organic compounds， the RFOs of AEM had different trends. For organic compounds with small size， with partially reversible adsorption， the RFOs of AEM did not change significantly； for organic compounds with larger size or terminal groups of smaller size， because of inserted adsorption， the RFOs of AEM were significantly reduced.



Preparation of Graphene Mediated Macrophage Membrane Coating and Its Effects on the Anti-fouling and Immunomodulatory Properties of Tianium Implants

LEI Jiahui, LUO Bin, SUN Xiaoqing, ZHANG Yujia, HU Xiaoqin, LAN Fang, WU Yao

2024, 45(3):  20230451.  doi:10.7503/cjcu20230451

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Titanium implants are susceptible to biofouling and inflammatory reactions， which can lead to poor bone fusion and implant failure. In this paper， we fixed graphene to the surface of titanium implant by polydopamine and then bound the M₂ macrophage membrane to the graphene surface via the extremely strong interaction force between graphene and phospholipid in the cell membrane to create a bioactive cell membrane coating at the macroscopic level. This homogeneous cell membrane coating has excellent resistance to biological contamination， which can effectively prevent non-specific adsorption of proteins. Titanium implants with cell membrane coatings showed excellent biocompatibility due to the high cellular affinity of native cell membranes. In addition， immunofluorescence and RT-qPCR（Real-time quantitative polymerase chain reaction） were used for detection of proinflammatory markers（iNOS， TNF-α） and anti-inflammatory markers（IL-10， IL-1ra）. In an inflammatory environment， the experimental results showed that the modified cell membrane-coated titanium implants could induce the polarization of macrophages to M₂ type and had excellent immunomodulatory ability. This cell membrane coating preparation strategy， relying on the interaction force between graphene and phospholipids， provides ideas for solving the problems of bio-contamination and inflammatory response of titanium implants.



Analytical Chemistry

Aqueous Two-phase Extraction Based on Deep Eutectic Solvents Coupled with UPLC for the Analysis of Heterocyclic Aromatic Amines in Urine of Smokers

LI Min, HE Shanshan, WANG Hongyu, ZHUANG Jiaying, JIN Yongri, LI Xuwen

2024, 45(3):  20230469.  doi:10.7503/cjcu20230469

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To assess the exposure to heterocyclic aromatic amines（HAAs） from tobacco smoke， a novel method， an aqueous two-phase system based on deep eutectic solvent（DES-APTS） followed by UPLC， was described to analyze five HAAs（IQ， IQ［4，5-b］， Harman， Norharman， Phe-P-1） from the urine samples of smokers. Seven kinds of choline chloride（ChCl）-based DESs had been synthesized and characterized by ¹H NMR and FTIR spectra. The significant parameters affecting the extraction efficiency of HAAs in the DES-ATPS procedure were systematically investigated. Under optimal extraction conditions， the recoveries for the target HAAs ranged from 81.9% to 106.2%. The obtained intra- and inter-day relative standard deviations（RSDs） were less than 2.9% and 3.2%， respectively. The detection limits（LODs） and quantification limits（LOQs） were obtained in ranges of 0.020—0.097 ng/g and 0.19—0.39 ng/g， respectively. The developed method of DES-ATPS， with its simplicity， good environment-friendliness and low-cost per sample， could be a promising alternative technique for rapidly extracting and quantifying HAAs from urine samples， and displayed great development potential in the field of the detection in biological samples.



The Method of Measuring Particle Size Distribution of Layered Double Hydroxides（LDHs） Using Ultrasonic Attenuation Spectroscopy

ZHANG Mingfeng, WU Bo, HOU Guanghao, ZHOU Lei, WANG Xuezhong

2024, 45(3):  20230463.  doi:10.7503/cjcu20230463

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Layered double hydroxides（LDHs）， as a high-performance non-precious metal electrocatalyst， possess remarkable advantages in enhancing the oxygen evolution rate and reducing hydrogen production costs. The particle size of LDHs directly impacts the effective exposed surface area and intrinsic structure of catalytically active sites， thereby significantly influencing the activity duration and catalytic efficiency of LDHs in the electrocatalytic oxygen evolution reaction. Consequently， achieving online detection of LDHs particle size distribution holds significant importance for controlling LDHs synthesis and enhancing their catalytic activity. Based on the unique characteristics of LDHs， such as small particle size and distinctive morphology， this study introduces a novel approach for online measurement of particle size distribution（PSD） in LDHs suspensions via ultrasonic attenuation spectroscopy， marking the first-time application of this method in the field of LDHs particle characterization. The principal challenge in measuring the PSD of LDHs suspensions using ultrasonic attenuation spectroscopy lies in the requirement of system-specific properties for both the dispersed and continuous phases， which are often elusive to acquire. To address this challenge， this research utilizes principal component analysis（PCA） in conjunction with error backpropagation（BP） neural networks to establish a predictive model. Additionally， by incorporating genetic algorithm（GA） for model optimization， the challenges associated with ultrasonic attenuation spectroscopy are successfully addressed. The model is validated using a CoFeAl-LDHs suspension system. The results demonstrate the effectiveness of the PCA-GA-BP neural network in the online prediction of LDHs particle size distribution within the suspension system. The predicted values exhibit a high degree of resemblance to the true values in terms of peak shape， displaying minimal deviation in peak height. The mean squared error（MSE） between the predicted and true values is calculated as 0.1497， and the model fitting coefficient R² stands at 0.9768， thus indicating the efficacy of this method as an accurate approach for online measurement of LDHs particle size distribution.



Preparation of Macroporous Weak Cation Exchange Chromatography Medium with High Capacity through “Grafting from” Method

GUO Wang, JIANG Zeping, MA Lei, QIAO Juan, MO Wenqing, JIN Haibo, HE Guangxiang, HUANG Yongdong, ZHANG Rongyue

2024, 45(3):  20230487.  doi:10.7503/cjcu20230487

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Macroporous polymer chromatography medium has a low protein binding capacity due to its large pore size and low surface area. To solve this problem， the weak cation exchange chromatography medium with high capacity was prepared through the grafting polymerization of methacrylic acid on the macroporous polyacrylate microspheres， which was initiated by redox reaction. The reaction factors were evaluated and the general rules between these factors and proteins binding capacity were obtained， including monomer concentration， potassium persulfate concentration and reaction temperature. The static binding capacity and dynamic binding capacity of the obtained medium reached 252.21 and 157.25 mg/mL， respectively. It was also found that the medium with a certain ion exchange capacity could maintain 100 mg/mL protein binding capacity in 0.2 mol/L NaCl buffer. The chromatographic medium was used for the purification of lysozyme in egg white， and high purification efficiency was obtained.



Organic Chemistry

Thermal Activation Delayed Fluorescence Materials Based on 2-Cyanopyridine Electron Receptors

WANG Qingsong, ZHANG Fujun, XU Huihui, CHEN Sihan, ZHANG Qianfeng, TONG Bihai, CHEN Ping, KONG Hui

2024, 45(3):  20230470.  doi:10.7503/cjcu20230470

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Four luminescent materials with 2-cyanopyridine as electron acceptor were synthesized， and the effects of different electron donors on the luminescent properties of these materials were investigated. In the single crystal structure of compound 5-（10H-phenothiazin-10-yl）picolinonitrile（PTPN）， the intermolecular hydrogen bond between the pyridine ring and the C—H···π intermolecular interaction between the phenothiazine group form a coplanar molecular configuration between the pyridine ring and the thiophene group， causing its luminescence to blue-shift from 520 nm in the thin film to 400 nm. The luminescence wavelengths of four compounds in polymethyl methacrylate（PMMA） thin films range from 434 to 520 nm. The photoluminescence quantum yields（PLQYs） of 5-（10H-phenoxazin-10-yl）picolinonitrile（PXPN）， PTPN and 5-［9，9-dimethylacridin-10（9H）-yl］picolinonitrile（DAPN）， which are thermally activated delayed fluorescence（TADF） emission， ranges from 0.17 to 0.57. Their delayed fluorescence lifetimes range from 4.1 to 5.3 μs. The values of ΔE_ST are between 0.045 and 0.069 eV. The PLQY of 5-（3，6-di-tert-butyl-9H-carbazol-9-yl）picolinonitrile（BCPN） is 0.91， and its luminescence lifetime is 12.4 ns， indicating fluorescence emission. Electroluminescent device tests have shown that these materials emit green light. The device based on DAPN had the best overall device performance. The maximum brightness of the doped device can reach 2855 cd/m²， and the peak current efficiency（CE）， power efficiency（PE） and external quantum efficiency（EQE） are 37.6 cd/A， 12.6 lm/W and 10.4%， respectively. The device based on BCPN has formed an efficient electroplex with a maximum brightness of 2367 cd/m²， and peak CE， PE and EQE are 29.3 cd/A， 11.5 lm/W and 9.4%， respectively. This study indicates that cyanopyridine receptors can form stable intermolecular hydrogen bonds and can be used for the development of TADF materials.



Manganese-induced Radical Cyclization of 1-Isocyano-2- ［1-（trifluoromethyl）ethenyl］benzenes to Access 4-CF₃-Quinoline Derivatives

YAO Tuanli, WANG Ke, ZHU Shuang, LI Tao

2024, 45(3):  20230448.  doi:10.7503/cjcu20230448

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A new Mn（Ⅲ）/Mn（Ⅱ） induced reaction was developed， which involves a radical 6-endo-trig cyclization of 1-isocyano-2-［1-（trifluoromethyl）vinyl］benzene with arylboronic acid and catalyzed by manganese. Various 4-CF₃-2 arylquinolines were obtained with high regioselectivity， chemical selectivity and mild condition without any external oxidants， ligands， or additives.



Physical Chemistry

Construction of EI/P25/Zr-MOFs Heterojunction and Its Performance for Photocatalytic Hydrogen Production

MOU Di, WU Haiyang, ZHANG Nanqi, AN Zhaokun, HE Xuan, ZHANG Fuqing, ZHAO Lei, CHEN Hui, FANG Wei, DU Xing, WANG Daheng, LI Weixin

2024, 45(3):  20230468.  doi:10.7503/cjcu20230468

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UiO-66-NH₂（NUO） has been used for photocatalytic hydrogen generation due to its excellent water stability， but its hydrogen production efficiency still needs to be improved. In this paper， EI/P25/NUO heterojunction was synthesized by adding 2-（2-fluorenyl）-4，5-1-bromodiphenyl-imidazole（EI） and P25 in NUO precursor solution via hydrothermal method. Compared with single Zr-MOFs and binary EI/NUO， the visible-light-driven photocatalytic hydrogen production rate of the EI/P25/NUO heterojunction can reach 6530.60 μmol·g^-1·h^-1， which is 304 times and 34 times higher than that of NUO and EI/NUO， respectively. This is because the introduction of EI can effectively improve the concentration of photogenerated carriers in the system， and the electron transport layer P25 can promote the transfer of photogenerated electrons generated by EI to NUO， reduce the recombination probability of photogenerated carriers， and further improve the performance of photocatalytic water decomposition for hydrogen production.



Mechanism of Molecular Oxygen Activation Mediated by Hydroxyl Groups on the Surface of Red Clay

DU Qing, NIU Huibin, XU Yan, ZHANG Jing, LAN Xing, HUANG Yingping, TAN Yunzhi, CHEN Xiaoting, FANG Yanfen

2024, 45(3):  20230422.  doi:10.7503/cjcu20230422

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The activation mechanism of molecular oxygen（O₂） by surface hydroxyl groups（Me-OH， Me=Al， Si， Fe） of natural clay minerals is still unclear. In this study， red clay（R-Clay） was heat-treated at varying temperatures in N₂ to adjust the number and shape of Me-OH sites on its surface， thus activating O₂ to different degrees for tetracycline（TC） degradation in water. As the temperature increased， the kaolin structure in R-Clay was gradually destroyed， and the Fe₂O₃ structure became more prominent. Among them， Me-OH on the surface of red clay （R-Clay₄₀₀） exists in the form of Al-Al-OH and Al-Si-OH， which efficiently degraded（86.36%） and mineralized TC（40%， 6 h）. Under visible light irradiation， both oxygen atoms and TC molecules on R-Clay₄₀₀ Si-O-Al can be used as electron donors to transfer photogenerated electrons（e^-） to O₂ adsorbed on the surface of R-Clay₄₀₀ to form superoxide radical（^•O₂^-） and singlet oxygen（¹O₂）， thus achieving efficient degradation of TC. Here， the surface Me-OH， used as the Brönsted site， adsorbs O₂ by hydrogen bond， which promotes electron transfer rather than traditional electron donor. This study further clarified the activation mechanism of clay minerals to O₂ and promoted the development of related research fields of mineral-based materials.



Application of Covalent Organic Frameworks in High-performance Lithium-ion Battery Anode Materials

ZHANG Jinkai, LI Jiali, LIU Xiaoming, MU Ying

2024, 45(3):  20230523.  doi:10.7503/cjcu20230523

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In this work， two covalent organic frameworks（COF-1， COF-2） with high thermal stability， good crystallinity， and large specific surface area were prepared through polycondensation. When used as anode materials for lithium-ion batteries（LIBs）， they exhibited high reversible capacities（charging specific capacities after 150 cycles， COF-1： 484 mA·h/g and COF-2： 327 mA·h/g， respectively）， excellent rate performance（reversible capacities at 2 and 10 A/g current densities， COF-1： 296， 180 mA·h/g， and COF-2： 265， 166 mA·h/g， respectively） ， working capacity under extremely high current density（charging specific capacities for 2000 cycles of 5 A/g current density， COF-1： 572 mA·h/g， COF-2： 332 mA·h/g） and operating performance under extreme temperatures（charging specific capacities after 40 cycles in 50 and ‒15 ℃ environments， COF-1： 2101， 218 mA·h/g， COF-2： 1760， 172 mA·h/g）. In addition， both types of COFs have the ability to activate electrochemical active groups as charging and discharging continue. COF-1 and COF-2 were cycled 400 times without adding conductive agents， and the charging specific capacity increases from 23 and 16 mA·h/g to 45 and 31 mA·h/g， respectively. And through the analysis of experimental data， we prove that under the conditions of high current density or high temperature environment， which can accelerate the ion diffusion rate， the activation effect is more favorable. By comparing these two types of COF materials， we also found that COF-1 with triazine ring structures has better lithium storage performance and electrochemical reaction kinetics than COF-2 with all benzene ring structures， indicating that C=N in the aromatic ring may be a group with high electrochemical activity.



Materials Chemistry

Preparation of Adsorption-degradation Collagen/ZnO Composites Based on Chrome-tanned Leather Shavings

TIAN Zhenhua, GAO Panpan, YU Ruohong, ZHAO Wenjie

2024, 45(3):  20230416.  doi:10.7503/cjcu20230416

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The utilization of hazardous waste chrome-tanned leather shavings is a difficult problem in the leather industry. Collagen， the main component of chrome-tanned leather shavings， can be used as adsorbent material； however， its application in the wastewater treatment field is limited due to the low stability and subsequent desorption challenges. In this paper， adsorption-degradation collagen/ZnO composites were prepared by in⁃situ loading of zinc oxide nanoparticles（ZnO） on collagen fibrils extracted from chrome-tanned leather shavings via acid methods. The infrared and X-ray diffraction spectra showed that ZnO with sheet hexagonal wurtzite structure was successfully loaded； meanwhile， its own photoresponse range was unaffected and the forbidden bandwidth was 3.20 eV. When the concentration of zinc precursor solution was 0.12 mol/L， the pH value of collagen fibril dispersion liquid was 8 and the mass of collagen sponge was 60 mg， the photocatalytic degradation of the composite was the best； namely， the degradation ratio of 10 mg/L methylene blue（MB） reached 95.2 % within 160 min and still reached 87.5% after five cycles. The fitting results of the kinetic models showed that the adsorption of MB by the composites was according with the pseudo-second-order adsorption kinetic model， which was controlled by chemisorption； moreover， the photocatalytic degradation of MB obeyed the first-order degradation kinetic model， and the highest degradation rate was 0.0172 min^-1. Additionally， the introduction of ZnO enhanced the antimicrobial property and thermal stability of the collagen/ZnO composites.



Polymer Chemistry

Pillaring Hydrogen Bonded Dense Structures of Chitosan for the Biosafe High-performance Humectant

GAO Nan, ZHENG Yue, LI Huanhuan, ZANG Wanchen, YUAN Ye, YANG Yajie, JIN Zhe

2024, 45(3):  20230426.  doi:10.7503/cjcu20230426

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Humectants with a large number of hydrophilic groups are able to increase or maintain the water content of a substance for a long time， which possess a huge range of applications in industries including medical care， food， cosmetic products， and medicinal herbs. Chitosan molecules featuring a variety of advantages of biodegradability， non-toxicity， anti-bacterial， etc， are investigated to be a high-performance humectant. Nevertheless， the dense structure originated from multiple hydrogen bonds leads to the inability of water molecules to access in the interior of the particles， which seriously depresses the material’s ability to absorb and store water. In this paper， a covalent coupling approach was adopted to react benzoic acid with chitosan through a dehydration polymerization reaction. The hydrophobic phenyl units are able to columnarize the hydrophilic chitosan chains， forming a large-volume space for the storage of the water molecules. Based on this， the specific surface area of the as-prepared material is enhanced by about 1000% compared to the original chitosan； correspondingly the water-absorption capacity has been increased by about 400%. At the same time， cellular safety tests have shown that the chitosan-based porous humectant possesses good biosafety properties. After uniformly distributed on top of the damping papers， the amount of water loss of the paper is improved by 20% compared to the commercial humectant， propylene glycol.



Synthesis of O-quaternary Ammonium Salt-oxidized Chitosan and Its Antibacterial Finishing for Cotton Fabric

ZHOU Xiaolong, WANG Ruiqi, CHEN Guoli, GUO Wenming, CHEN Fei, ZHOU Yan, SUN Lide, TANG Dabao, XU Yunhui

2024, 45(3):  20230375.  doi:10.7503/cjcu20230375

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By utilizing vanillin to form Schiff bases with the C2 amino group of chitosan in order to protect the amino group， and then grafting 2，3-epoxypropyl trimethylammonium chloride（GTA） quaternary ammonium salt on C6 site in chitosan， O-quaternary ammonium chitosan（O-HACC） was synthesized after removing Schiff-base from the solution of dilute HCl and ethanol. Subsequently partial groups at C2 and C3 positions in O-HACC were selectively oxidized into dialdehyde groups with KIO₄， so the O-quaternary ammonium salt-oxidized chitosan（O-HAOCC） was finally obtained， which possessed the fiber-reactive and dual antibacterial activities， and then grafted with cotton fabric to obtain O-HAOCC modified cotton fabric. The characterizations of Fourier-transform infrared spectroscopy（FTIR）， X-ray diffraction（XRD）， proton nuclear magnetic resonance spectroscopy（¹H NMR）， scanning electron microscopy（SEM） and differential scanning calorimetry（DSC） displayed that， major amino groups were retained while introducing the structure of quaternary ammonium salt and active dialdehyde groups in O-HAOCC molecules， and the crystal morphology was destroyed， as well as thermal stability reduced. Furthermore， the test results showed that the water solubility of O-HAOCC oxidized for 3 h achieved 23.7 g/100 mL， and the 2，2'-azinobis（3-ethylbenzothiazoline-6-sulfonic acid）diamine salt（ABTS） radical scavenging rate after 40 min was 65.58%. The graft ratio of O-HAOCC modified cotton fabric arrived at 9.84% when the mass fraction of O-HAOCC was 2%， the reaction time was 2 h and the graft temperature was 80 ℃. The antibacterial rate of modified cotton fabrics against Staphylococcus aureus and Escherichia coli was 98.63% and 93.38%， respectively， furthermore the antibacterial rate maintained above 90.75% after 50 times of washing， manifesting extensive application in antibacterial textile and garment， home textile and medical and sanitary products， etc.