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10 October 2022, Volume 43 Issue 10

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Content

Cover and Content of Chemical Journal of Chinese Universities Vol.43 No.10(2022)

2022, 43(10):  1-8. 

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Review

Inorganic-based Surface Materials with Anti-SARS-CoV-2 Properties and Their Mechanisms of Action

LI Dan, XIAO Liping, FAN Jie

2022, 43(10):  20220301.  doi:10.7503/cjcu20220301

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The COVID-19 outbreak caused by SARS-CoV-2 has posed a serious threat to human health. The widespread of the virus has increased the demand for anti-virus surface materials， especially in public places. This article reviews a series of inorganic surface materials with antiviral properties， including metals and its derivatives， graphene and its derivatives， and zeolites， and their antiviral mechanisms. The challenges and development prospects are summarized and prospected.



Layered Double Hydroxides as Sorbent for Remediation of Radioactive Wastewater

ZHENG Meiqi, MAO Fangqi, KONG Xianggui, DUAN Xue

2022, 43(10):  20220456.  doi:10.7503/cjcu20220456

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Nuclear energy has become an important part of energy structure for our country， however， it is still a big challenge to settle the problems of radioactive wastewater. Layered double hydroxides（LDHs） is a kind of anionic clay materials， which have been attracted much attention in the treatment of radionuclide-containing wastewater due to its controllable composition， adjustable anionic types， large specific surface area， tunable particle size and morphology. In this paper， we mainly focused on the adsorption behavior and mechanism of LDHs for radioactive wastewater. Besides， several key challenges in using LDHs as sorbents for capture of radioactive ions are presented. We hope that this work could shed light on the sustainable development of LDHs as amendment for radioactive wastewater in future.



Supramolecular Interactions-mediated Nanodrug Nucleation

XU Wenzhe, ZHANG Hao

2022, 43(10):  20220264.  doi:10.7503/cjcu20220264

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Nanoprecipitation， referring to the formation process of nanometer-sized particles from supersaturated system， is the workhorse for preparing novel nanodrugs because of the flexibility to manipulate nucleation and/or growth processes by extensively selecting the species of drugs， solvents， carriers， surfactants， and other excipients. Carrier-free nanodrugs（CFNs） have been prepared via nanoprecipitation strategy， while a variety of intermolecular weak interactions between drug molecules， typically π?π stacking and hydrophobic interaction， are dominant in the nucleation of CFNs. However， the specific roles， synergistic effects， and in particular the manipulation of these supramolecular interactions during nucleation have never been summarized. In this review， the predominant contribution of supramolecular interactions in the nucleation of CFNs is proposed according to the classical nucleation theory of nanoprecipitation firstly. Next， on the basis of the great progresses in single-drug self-assembled CFNs， the advantages of multidrug co-assembled CFNs are highlighted. In addition， supramolecular interactions-mediated nucleation is further expanded to the CFNs constructed through metal ions-involved coordination. This overview theoretically elucidates the role of supramolecular interactions in the nucleation of nanodrugs， which will undoubtedly promote the development of next-generation CFNs characterized with bio-safety， multi-functionality， and combination therapy.



Porous Materials Inspired by Microbial Fermentation： Preparation Method and Application

TIAN Xiaokang, ZHANG Qingsong, YANG Shulin, BAI Jie, CHEN Bingjie, PAN Jie, CHEN Li, WEI Yen

2022, 43(10):  20220216.  doi:10.7503/cjcu20220216

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As a novel method of obtaining porous materials， microbial fermentation combining microbial fermentation engineering with foaming engineering has attracted wide attention on account of overcoming the defects of the traditional preparation method， such as special equipment requirement， complex operation， complex post- processing， chemical pollution and high cost. Based on the research of porous materials inspired by microbial fermentation， the definition of porous materials， the classification of porous hydrogels and their preparation methods were summarized. Then， aiming at the preparation method of porous materials induced by microorganisms， the applications in dye adsorption， seawater evaporation desalination， electromagnetic shielding and preparation of new functional biomaterials were reviewed in detail. Finally， the future development of microbial inspired porous materials was prospected.



Article: Inorganic Chemistry

Controllable Syntheses of Two Cd（II） Metal-organic Frameworks Possessing Related Structures

XING Peiqi, LU Tong, LI Guanghua, WANG Liyan

2022, 43(10):  20220218.  doi:10.7503/cjcu20220218

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2，5-Dimethoxy-N，N'-bis（4-pyridyl）terephthalamide（abbreviated as dmbpt） was synthesized， and two new complexes， ［Cd₂（dmbpt）₂（Hbtc）₂］·2DMF·C₂H₇N·H₂O（1） and ［Cd₃（dmbpt）₂（btc）₂］·4H₂O（2）， were further prepared， in which dmbpt and 1，3，5-benzenetricarboxylic acid（abbreviated as H₃btc） were used as ligands. Complex 1 is a 2D metal-organic framework（MOF） with 3，5L2 topology. Complex 2 is a 3D MOF with jcr7 topology， which is a rare topology. Both two complexes contain the secondary building unit， Cd₂（—COO）₄（—Py）₄. Regarding structural relations， the 3D framework of complex 2 may be regarded as coordinate-bonded 2D frameworks， which can be found in complex 1. Under the solvothermal condition with the same reactants and solvents， two complexes can be simultaneously produced with different ratios. The ratio of complex 1 to complex 2 in the product can be controlled by changing the concentration of the reactants. This may be attributed to the effect of dimethylamine， which was generated by the decomposition of DMF， on the deprotonation of H₃btc.



Synthesis， Characterization and Catalytic Oxidation Iodine Ion Performance of trz-Cl-Cu-PMo₁₂

ZHANG Taiwen, GUO Jun, ZHANG Dan, YUAN Changmei, QIU Shuangyan

2022, 43(10):  20220215.  doi:10.7503/cjcu20220215

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Using H₃PMo₁₂O₄₀ as precursor， 1，2，4-triazole-modified Keggin-type polyoxometalate-based metal- organic framework compound trz-Cl-Cu-PMo₁₂ was synthesized by in situ decarboxylation of 1，2，4-triazole-3-carbo?xylic acid by hydrothermal method. It was characterized by X-ray single crystal diffraction， IR， TG， XRD， SEM， elemental analysis， etc. X-ray single crystal diffraction and elemental analysis showed that the structural formula of the crystalline compound is ［Cu₆Cl_0.5（C₂H₂N₃）₄］［PMo₁₂O₄₀］［Cu₆Cl_0.5（C₂H₂N₃）₄］， and consists of one classic Keggin type ［PMo₁₂O₄₀］^3-， two ［Cu₆Cl_0.5（C₂H₂N₃）₄］^1.5+ by approximately center symmetry， and one-dimen?sional（1D）to three-dimensional（3D）structures are formed between components through supramolecular interactions. Catalytic stu-dies show that the heterogeneous catalyst is in catalytic oxidation of hydrogen peroxide with iodide ion as iodine element， the reaction rate reaches the end point after 4 min 35 s， the reaction rate is as high as 1.42×10^-5 mol·L^-1·s^-1， and the generation rate of iodine element is increased by about 551 times. The catalyst is reused 8 times， and the conversion rate is still as high as 99. 6%， showing excellent catalytic activity and good repeatability.



Pd-loaded Defective TiO₂ Nanotube Arrays for Enhanced Photocatalytic Hydrogen Production Performance

JIANG Shan, SHEN Qianqian, LI Qi, JIA Husheng, XUE Jinbo

2022, 43(10):  20220206.  doi:10.7503/cjcu20220206

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Pd-TNT-Ni catalysts with different metal Pd contents were obtained on Ni-doped defective state TiO₂ nanotube arrays（TNT-Ni） by photoreductive deposition method through oxygen vacancy induction. SEM， XPS， UV-Vis DRS， surface photovoltage（SPV）， PL and electrochemical tests were employed to investigate the effect of strong interactions between Pd and Ni-doped defective state TiO₂ nanotube arrays on their optical absorption properties and carrier separation and transport efficiency. The modulation mechanism of strong interaction on the regulation of the photocatalytic activity of the material was elucidated， and the action mechanism of Pd-enhanced Pd-TNT-Ni photocatalytic performance was proposed. The results demonstrated that the Pd nanoparticles prepared by photoreduction were 10—20 nm in size. The photoresponse of the Pd₁₂₀-TNT-Ni sample showed 4.22 mA/cm²， which was 3.7 times higher than that of the unloaded TNT-Ni sample（1.14 mA/cm²）. Meanwhile， Pd₁₂₀-TNT-Ni had the most excellent average hydrogen production rate（5.16 mmol·g^?1·h^?1）， which was nearly 12 times higher than that of the TNT catalyst（0.45 mmol·g^?1·h^?1）. It was shown that the strong interaction between Pd and defective TiO₂ nanotube arrays drove carrier separation and transport， while Pd as an electron trap and reactive site significantly improved the photocatalytic performance of the material， which had implications for the design and preparation of semiconductor materials with high photocatalytic activity.



Preparation of Au-CeZr/FAU Catalytic Membranes for Preferential Oxidation of CO in H₂-rich Stream

WEI Lina, PENG Li, ZHU Feng, GU Pengfei, GU Xuehong

2022, 43(10):  20220175.  doi:10.7503/cjcu20220175

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A series of CeZr/FAU zeolite membranes with different Ce/Zr doping ratios was prepared by impregnation method， and further loaded with nano-gold to prepare Au-CeZr/FAU catalytic membranes. The obtained membranes were well characterized， and their catalytic performances toward the preferential oxidation of CO in H₂-rich gases were studied. The H₂-TPR analysis showed that the Au-Ce₁Zr₁/FAU membrane with Ce/Zr doping ratio of 1∶1 had the best redox ability， which benefited the dispersion and reduction of Au nanoparticles. The O₂-TPD analysis suggested that this membrane also possessed more active oxygen species. As a result， the Au-Ce₁Zr₁/FAU catalytic membrane exhibited the best catalytic activity for CO-PROX reaction with 100% CO conversion and 100% O₂ selectivity at low temperature of 60 ℃ as well as high stability for 10 thermal cycling tests.



Design， Synthesis and Photocatalytic Antibacterial Mechanism of Ag-AgVO₃/BiVO₄ Composite as a High-efficient and Broad-spectral Antibacterial Agent

SHAO Wenhui, HU Xin, SHANG Jing, LIN Feng, JIN Liming, QUAN Chunshan, ZHANG Yanmei, LI Jun

2022, 43(10):  20220132.  doi:10.7503/cjcu20220132

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A leaf-like Ag-AgVO₃/BiVO₄ photocatalyst with broad-spectrum disinfection activity under visible light irradiation was prepared. Detailed characterizations confirmed the formation of the composites and good optical properties. Using 3,3',5,5'-tetramethylbenzidine(TMB） oxidation as a model， the Ag-AgVO₃/BiVO₄ nanocomposites exhibited good oxidase-like activity which can convert O₂ into reactive oxygen species and oxidize TMB to ox-TMB in blue color. Furthermore， the nanocomposites demonstrated excellent antibacterial activity against Staphylococcus aureus and Escherichia coli， over 99% of both bacteria were killed in 4 min under visible light irradiation. More importantly， the antibacterial mechanism was systematically studied by a variety of experimental methods. Scavenger experiments of different reactive species proved that the photoinduced electrons generated at the oxidation site of Ag-AgVO₃/BiVO₄ play a key role as oxidative species. Results of fluorescent-based cell live/dead tests， SEM technology， and intracellular macromolecular substances and proteins assays confirmed that generated reactive oxygen species（ROS） could kill the bacteria by destroying the integrity of cell membrane and disrupting the cell metabolism. In addition， Ag-AgVO₃/BiVO₄ has a good antibacterial effect on nine pathogenic bacteria including Gram-positive bacteria， Gram-negative bacteria and fungi， indicating its broad-spectrum antibacterial property.



Analytical Chemistry

Synthesis， Two-photon Fluorescence Imaging and Photodynamic Therapy of Lysosome-targeted Indole-BODIPY Photosensitizer

LIU Miao, LIU Ruibo, LIU Badi, QIAN Ying

2022, 43(10):  20220326.  doi:10.7503/cjcu20220326

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A lysosome-targeted near-infrared photosensitizer（IMBDP-Lys） was synthesized through the Knoevenagel condensation reaction for two-photon fluorescence imaging and photodynamic therapy. IMBDP-Lys was a heavy atom-induced photosensitizer， which was constructed by two morpholine-indole functional groups attached to the 3-position and 8-position of the boron-dipyrromethene（BODIPY） core. Gaussian 09W software was used to calculate that the energy gap（of S₁ and T₂ states of the photosensitizer IMBDP-Lys was 0.12 eV， which can effectively promote the intersystem crossing（ISC）. In CH₂Cl₂ solution， the maximum absorption wavelength of photosensitizer IMBDP-Lys was 631 nm and the emission wavelength was 684 nm. With methylene blue as reference， the photosensitizer IMBDP-Lys had a larger singlet oxygen quantum yield of 48.3% under near infrared light. In addition， the photosensitizer IMBDP-Lys containing two morpholine groups has good biocompatibility and accurate targeting ability. It could quickly enter zebrafish for two-photon fluorescence imaging， and the co-localization coefficient with Lyso-Tracker Green dye was as high as 0.95. Thiazolyl blue tetrazolium bromide（MTT） assay showed that the photosensitizer had low dark toxicity（≥85%） and high photo-toxicity（IC₅₀ was 0.52 μmol/L）. Under the illumination of 660 nm， the reactive oxygen species（ROS） fluorescence probe 2'，7'-dichlorodihydrofluorescein diacetate（DCFH-DA） proved that the photosensitizer could produce ROS， meanwhile， AO/EB staining test and cell migration experiment showed that the generated ROS could not only induce A549 cell apoptosis， but also effectively inhibit tumor cell migration. Therefore， the near infrared photosensitizer IMBDP-Lys has great application potential in two-photon fluorescence imaging and lysosome-targeted photodynamic therapy.



In⁃situ Analysis of Interfacial Reaction Process Inside Li-Ga Liquid Metal Battery

WANG Wei, ZOU Bingchen, HOU Jie, ZHOU Wanli, LUO Jianping, WANG Kangli, JIANG Kai

2022, 43(10):  20220261.  doi:10.7503/cjcu20220261

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Due to the specific working mechanism of liquid metal battery（LMB）， substance change only happens at the cathode interface during charge and discharge process. For better understanding the dynamic property of mass transport process inside LMB noninvasively， the A-scan type ultrasonic pulse echo technology was used to investigate discharge process of 40 ℃ Li-Ga LMB. By comparing the change of ultrasonic echo signal before and after discharge， the acoustic pressure value with specific time of flight was identified as the signal reflected from the liquid Ga/electrolyte interface. The results show that the acoustic pressure value increases proportionally to the discharge capacity. When the solid Li₂Ga₇ interphase forms and entirely covers the liquid Ga cathode， the acoustic pressure value will finally increase about 45% compared with the original state. The quantitative relationship between discharge capacity and ultrasonic pressure value was calculated， which means that ultrasonic pulse echo signal can be used to diagnose discharge state of Li-Ga LMB. Moreover， in order to illustrate the mass transport mechanism at the liquid Ga cathode interface， the formation process of Li₂Ga₇ solid interphase at the initial stage of discharge process was recorded by ultrasonic confocal phased array three-dimensional imaging system. It was found that Li₂Ga₇ solid interphase firstly form at the central part of the liquid Ga cathode interface， which is in accordance with the optical result obtained after 1.4 mA·h capacity discharged. This work provides a novel in?situ and non-destructive interface analysis method for liquid metal battery.



Synthesis of Schiff-based Covalent Organic Framework and Its Recognition of I ^‒

WANG Di, ZHONG Keli, TANG Lijun, HOU Shuhua, LYU Chunxin

2022, 43(10):  20220115.  doi:10.7503/cjcu20220115

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A new type of covalent organic framework fluorescent probe， TpPa-COOH COF， is designed and synthesized. The probe can highly selectively recognize I^? in a solution of THF/H₂O（volume ratio of1∶1）. The color of the solution changed from light red to yellow after adding I^? to the probe solution which can be observed with the naked eye， and the fluorescence intensity is significantly reduced at 317 nm. The probe has a high selectivity with a detection limit of 0.028 μmol/L， and the pH range is wide（1~13）， which provids a good application prospect in I^? detection.



Organic Chemistry

Visible Light Induced Cyclization of O-Alkenylcarboxanilide to 2-Quinolinone

ZHANG Xiaofei, LIU Jiaxin

2022, 43(10):  20220274.  doi:10.7503/cjcu20220274

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A free radical cyclization reaction induced by visible light using cheap and readily available O-alkenylformanilide was developed. The strategy was used to synthesize fifteen 2-quinolinone derivatives in good to excellent yields. This method is simple and efficient， with mild conditions and excellent functional group compatibility. Meanwhile， a plausible mechanism is proposed on the basis of several mechanistic experiments and literature precedents. This method not only provides a new type of organic reaction involving O-alkenylformylanilide， but also provides a new pathway for the photocatalytic synthesis of quinolinones.



Synthesis， Structure and Characterization of a Dihydrophenazine Based 3D Covalent Organic Framework

WANG Kaixuan, LI Ziping, CHEN Xianyang, CUI Yong

2022, 43(10):  20220210.  doi:10.7503/cjcu20220210

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Dihydrophenazine derivatives have received considerable attention due to their unique redox activity. In this paper， a dihydrophenazine based monomer 5，10-di（4-formylphenyl）-5，10-dihydrophenazine（M1） was designed and synthesized， and 3D-PN-2 was then prepared with a Schiff-base reaction by the combination of M1 and tetrakis（4-aminophenyl）methane（TAM）. 3D-PN-2 was characterized by powder X-ray diffraction（PXRD）， nitrogen adsorption-desorption experiment， FTIR， ¹³C CP/MAS NMR， SEM and TEM. After combined with theoretical simulation， 3D-PN-2 was identified as a three-dimensional covalent organic framework（3D COF） with an 11-fold interpenetrated dia topology. Subsequent studies showed that 3D-PN-2 had good thermal and chemical stability. The optical absorption property of 3D-PN-2 was studied by UV-Vis diffuse reflectance spectrum. 3D-PN-2 exhibits broad absorption in the region from UV to visible light（absorption edge： 630 nm）， and the band gap of 3D-PN-2 is 2.11 eV. The redox property was studied by cyclic voltammetry， and the highest occupied molecular orbital（E_HOMO） and lowest unoccupied molecular orbital（E_LUMO） were calculated to be -4.50 and -2.39 eV， respectively. These results suggest that 3D-PN-2 will be a promising COF candidate for photocatalysis applications.



Physical Chemistry

A Dataset Representativeness Metric and A Slicing Sampling Strategy for the Kennard-Stone Algorithm

WU Qingying, ZHU Zhenyu, WU Jianming, XU Xin

2022, 43(10):  20220397.  doi:10.7503/cjcu20220397

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In machine learning with big data， it is essential to prepare a representative dataset for training a model. The Kennard-Stone（KS） algorithm and its derivatives are a large class of excellent dataset splitting methods. But it rely heavily on empirical selection or modeling results to determine the sampling ratio and sampling number. In addition， its computational complexity is \mathrm{O}\left(K^{\mathrm{3}}\right)\text{?} according to the original literature， making it difficult to apply to massive data. In this paper， we design a metric based on dataset completeness to quantify the representativeness degree of an extracted subset to the whole dataset. An amendment using dynamic programming algorithm is put to reduce the algorithm complexity to {\mathrm{O}}^{\text{'}}\left(K^{\mathrm{2}}\right). And a slicing sampling strategy is proposed to divide the whole dataset into several subset and implement KS sampling respectively， which can further improve the algorithm efficiency to {\mathrm{O}}^{\text{'}\text{'}}\left(K\right). The partial least squares regression test results show that the method can improve the sampling efficiency while still ensuring the representativeness of the finally extracted dataset.



Organic Chemistry

Dynamics Study of Intramolecular Vibrational Energy Redistribution in RDX Molecule

ZHANG Lingyu, ZHANG Jilong, QU Zexing

2022, 43(10):  20220393.  doi:10.7503/cjcu20220393

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In this paper， based on the Born-oppenheimer molecular dynamics（BOMD） simulations， the coupling matrix between different vibrational modes of cyclotrimethylene trinitramine（RDX） single molecule was constructed， and the optimal energy transfer pathways from low-frequency vibrational mode to high-frequency vibrational mode with different initiation energies were obtained. The results showed that the —NNO₂ group in RDX single molecule was more favorable for energy localization， while vibrational mode v₃ and vibrational mode v₄ played an important role in the energy transfer process from low-frequency vibrational mode to high-frequency vibrational mode. The further analysis for the two vibrational modes of v₃ and v₄ suggested that different initiation energy could lead to different energy transfer pathways for RDX single molecule. With the lower initiation energy， the RDX single molecule tended to follow the energy transfer pathway as， low-frequency vibrational mode → medium-frequency vibrational mode → high-frequency vibrational mode. With the higher initiation energy， the energy tended to transfer from the low-frequency vibrational mode to the high-frequency vibrational mode. This work reveals the detail mechanism of the intramolecular vibrational energy redistribution in single RDX molecule， and can be further applied in the investigation of other energy transfer process.



Physical Chemistry

Silicone Surfactant-enhanced Dual Networks and High Temperature Resistance Porous Silicone Elastomers

QIAO Zhenghua, FAN Qi, HAO Jingcheng

2022, 43(10):  20220384.  doi:10.7503/cjcu20220384

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A stable water-in-oil（W/O） emulsion was prepared by using polyether-modified trisiloxane surfactant， acrylate-modified silicone oil， and water. Porous organosilcone elastomers with double networks were produced after acid-base catalyzed hydrolysis， UV-initiated polymerization， and drying to remove water. Scanning electron microscope（SEM） images show that the elastomers have rich pore structures. Compressive strength tests clearly demonstrate that the elastomers have good compression resistance and still have good resilience performance under 45% compressive strain for 50 cycles. In addition， the prepared silicone elastomers have excellent high temperature resistance， and the decomposition temperature is 370 ℃， which is higher than the decomposition temperature of most silicone elastomers. The preparation technology of acrylate modified silicone oil is mature， cheap and easy to obtain， which significantly reduces the production cost of porous silicone elastomer， and provides a new idea and application prospect for large-scale development of silicone materials.



Vacuum Freeze Drying to Prepare Porous Carbon Based Composite Membranes for Efficient Solar Steam Generation

XU Xiaojian, LI Bo, LIN Mengxiao, ZHAN Shuo

2022, 43(10):  20220361.  doi:10.7503/cjcu20220361

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Multi walled carbon nanotubes（CNTs） and polyvinylidene fluoride（PVDF） were used as raw materials to form a uniformly blended colloid by phase conversion method. The colloid was solidified by vacuum freeze drying technology， and some solvents volatilized in vacuum to prepare CNTs/PVDF composite membrane with porous structure. The experiments show that the freeze dried CNTs/PVDF composite membrane has excellent light absorption ability and surface hydrophilicity. Under the illumination intensity of 1 kW/m²， the water evaporation rate can reach 1.95 kg·m^-2·h^-1 and the photothermal conversion efficiency is 92.9%. At the same time， the evaporator equipped with freeze dried CNTs/PVDF composite membrane shows good salt pollution resistance， significant stability and excellent solar evaporation performance when treating simulated seawater and dye wastewater. These results show that freeze dried CNTs/PVDF composite membrane will have a wide application prospect in freshwater acquisition， sewage treatment and other fields in the future.



Spectroscopic and Theoretical Studies on 5-Mercapto-1，3，4-thiadiazole-2-thione Microsolvation Clusters

WANG Yuanyue, AN Suosuo, ZHENG Xuming, ZHAO Yanying

2022, 43(10):  20220354.  doi:10.7503/cjcu20220354

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Microsolvation effect， namely solvation process， widely exists in all physical， chemical and life processes. In the liquid phase chemical reaction system， microsolvation effect is most fundamental for almost all chemical reactions. Crystalloid 5-mercapto-1，3，4-thiadiazole-2-thione（MTT） was characterized as thiol-thione monomer by Fourier transform Raman（FT-Raman） combined with density functional theoretical（DFT） calculation. Both the size and hydrogen bond sites of microsolvation clusters were confirmed in acetonitrile， methanol and water. UV-Vis absorption spectroscopic experiments revealed the effect of solvents and pH on the structures of MTT. Combined with density functional theory（DFT） calculations， the hydrogen bonding interactions between MTT and solvents contributed to the shifts of spectrum indicated. The MTT clusters in acetonitrile， methanol and water were preliminarily determined as MTT（CH₃CN）， MTT（CH₃OH）₂ and MTT（H₂O）₂ by optimizing the possible hydrogen-bonding cluster structures and calculating the total binding energy and average binding energy.



Preparation and Electrochemical Properties of N-CNTs/NiCo-LDH Composite

HOU Congcong, WANG Huiying, LI Tingting, ZHANG Zhiming, CHANG Chunrui, AN Libao

2022, 43(10):  20220351.  doi:10.7503/cjcu20220351

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Nitrogen-doped carbon nanotubes（N-CNTs） were prepared by carbonizing polypyrrole nanotubes at high temperature， and nickel-cobalt layered double hydroxides（NiCo-LDH） were in situ grown on N-CNTs by coprecipitation method to produce N-CNTs/NiCo-LDH composite with three-dimensional interconnected network structure. The effect of different nickel/cobalt molar ratios on the morphology， structure and electrochemical properties of N-CNTs/NiCo-LDH composite was investigated. The results showed that N-CNTs/Ni₁Co₂-LDH had the best electrochemical performance when the molar ratio of nickel/cobalt was 1∶2. The specific capacitance can reach 1311.8 F/g at a current density of 1 A/g. When the current density was 10 A/g， the capacitance retention rate of N-CNTs/Ni₁Co₂-LDH was as high as 88.3%， showing excellent rate capability. After 2500 cycles， the capacitance retention rate of N-CNTs/Ni₁Co₂-LDH can still reach 76.4%， revealing good cycling stability. In addition， the N-CNTs/Ni₁Co₂-LDH//AC aqueous hybrid supercapacitor assembled by using N-CNTs/Ni₁Co₂-LDH and activated carbon（AC） electrodes had a high energy density of 27.19 W·h/kg at 750 W/kg power density. The exceptional electrochemical performance indicated that N-CNTs/Ni₁Co₂-LDH composite had broad application prospects in energy storage.



Theoretical Study on the Fragmentation Mechanism of CH₃SSCH₃ Radical Cation Initiated by OH Radical

CHENG Yuanyuan, XI Biying

2022, 43(10):  20220271.  doi:10.7503/cjcu20220271

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The fragmentation mechanism of CH₃SSCH₃ radical cation（CH₃SSC{\mathrm{H}}_{\mathrm{3}}^{?}⁺， DMDS^?+） initiated by OH radical（·OH） in the gas phase， toluene， and water was studied at the UωB97X-D/6-311+G^** level. The influence of solvent effect on the reaction was discussed. The results show that DMDS^·+ firstly reacts with ·OH to form the radical coupling product CH₃S（OH）SCH₃⁺（R1） or the hydrogen abstraction product complex［CH₂=SSCH₃+H₂O］⁺（R2）. Then， cleavage of S—S bond concerted proton transfer directly occurs for the fragmentation of R1. While， conformational change， carbophilic addition to C=S double bond and cleavage of S—S bond concerted proton transfer occur in turn for the fragmentation of R2. Deprotonated products are CH₃SOH， CH₂=S， and HSCH₂OH. Toluene slightly reduces the free energy barrier of the rate determining step in the fragmentation reaction. Water solvent is favorable for the fragmentation of R1， but unfavorable for the fragmentation of R2， especially an explicit water molecule participates in the reaction. In the gas phase， toluene， and water， with ·OH and DMDS^·+ as initial reactant， although the free energy barriers of the rate determining steps are 167.6—202.8 kJ/mol， the fragmentation reactions are all exothermice reactions（?154.3— ?31.4 kJ/mol）.



Preparation of Nano-copper Modified Three-dimensional Zinc Mesh Electrode and Its Performance as Anode for Zinc-ion Batteries

JIANG Baozheng, HUANG Wenting, LIU Wenbao, GUO Rongsheng, XU Chengjun, KANG Feiyu

2022, 43(10):  20220257.  doi:10.7503/cjcu20220257

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Nano-copper modified three-dimensional zinc mesh（nano Cu@3D Zn mesh， denoted as 3D Cu-Zn） electrode was designed and fabricated. The 3D Cu-Zn electrode was adopted as the host material of Zn deposition in zinc ion batteries. Stable Zn anode with long cycle life was achieved. The 3D Cu-Zn electrode with 3D zinc mesh skeleton and uniformly distributed Cu nanoparticles with 3D dendritic morphology can reduce the local current density and provide structural support and accommodation space for Zn deposition. In addition， the copper with strong zinc binding ability on the surface of the zinc mesh and subsequent in situ formed Cu-Zn alloy can effectively reduce the nucleation overpotential and act as uniformly distributed nucleation sites to guide the uniform nucleation and deposition of zinc. The 3D Cu-Zn electrode exhibits low nucleation overpotential and interfacial impedance， and shows excellent cycling stability（over 1100 h lifespan） in symmetric cells at a current density of 0.5 mA/cm². When combined with MnO₂ cathode， the full cell with 3D Cu-Zn electrode exhibits smaller polarization， superior rate performance and excellent cycling performance.



Effects of Electron Energy on the Chemical Products of Surface Dielectric Barrier Discharge Plasma

LIU Kun, ZUO Jie, LI Hua, XIANG Hongfu, RAN Congfu, YANG Minghao, GENG Wenqiang

2022, 43(10):  20220249.  doi:10.7503/cjcu20220249

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A dual-channel optical detection system without trigger signal was developed based on photomultiplier tube， and a test prototype was established to accomplish the measurement of the approximate electric field of surface dielectric barrier discharge（SDBD） plasma， thus allowing the determination of the electron energy by the BOLSIG+ software. In addition， the changes of chemical products in SDBD plasma at different voltages and frequencies were researched by in?situ UV absorption spectrum and Fourier transform infrared spectrum. On this basis， the micro? scopic mechanism of product interaction was analyzed in conjunction with the plasma chemical reactions. The results indicated that the electron energy could change the rate coefficient of electron collision reactions and regulate the concentration of reactive particles which are the source of chemical reactions， thus affecting the generation and quenching of chemical products. Therefore， the present study contributes to a better understanding of the physico-chemical processes in low-temperature plasmas and provides a referable scientific and theoretical basis for the regulation of plasma products applications.



Enhanced Catalytic Performance of Supported Nano-gold by the Localized Surface Plasmon Resonance for Selective Hydrogenation of Butadiene

LI Xueyu, WANG Zhao, CHEN Ya, LI Keke, LI Jianquan, JIN Shunjing, CHEN Lihua, SU Baolian

2022, 43(10):  20220174.  doi:10.7503/cjcu20220174

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During the polymerization of mono-olefins to prepare polymers， impurities such as alkynes and diolefins can poison the polymerization catalyst. Fossil energy driven thermocatalytic selective hydrogenation is the main impurity removal in the industry， which is a high energy consumption and high pollution process. The development of novel green and low-energy reaction pathways is one of the urgent problems in the current industry. Based on the plasmon resonance effect of metal nanoparticles， converting light energy into thermal energy to drive industrial catalytic hydrogenation is a very promising option. In this study， graphene oxide loaded gold（Au） catalysts（Au/GO） were prepared by cationic adsorption method， and the Au loading（mass fraction 0.2%—2%） was adjusted to achieve controllable preparation of Au in the particle size of 10—21 nm. The efficiency of photo-thermal conversion of Au/GO was as high as 88%. Using the selective catalytic hydrogenation of butadiene as a probe reaction， it was found that under 0.2 W/cm² illumination conditions， the conversion of butadiene increased and then decreased with increasing loading， and the butene selectivity was above 90%. Particularly， Au/GO-0.5 exhibited high butadiene conversion （99%） and butene selectivity（90%） at a gold loading of 0.5%（particle size ca. 15 nm） and a photothermal conversion temperature of 100 ℃. More importantly， the catalyst showed no deactivation trend after 144 h stability test. In addition， the photo-thermal driven catalytic activity developed in this work was improved by a factor of 5 compared to the thermal catalytic reaction under the same conditions. The analysis by in situ X-ray photoelectron spectroscopy（XPS） tests showed that this improvement in catalytic performance was mainly derived from the large number of Au ^δ+ active sites generated on the excited nanogold surface during the plasma photo-transfer thermal process. This study provides a green and efficient reaction pathway for the selective catalytic hydrogenation of industrial unsaturated olefins.



Synthesis of Hierarchical Porous Aromatic Frameworks for Immobilization of Thiourea Catalyst

SUN Jinshi, CHEN Peng, JING Liping, SUN Fuxing, LIU Jia

2022, 43(10):  20220171.  doi:10.7503/cjcu20220171

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A hierarchical porous aromatic framework（PAF-70） was synthesized via a new synthetic strategy. Nitrogen adsorption-desorption isotherms showed that PAF-70 had mesoporous structure with narrowly distributed pore size. The pore width of PAF-70 was 3.8 nm， which agreed well with the simulation value（ca. 3.7 nm）. Thermogravimetric analysis displayed good thermal stability of PAF-70. Furthermore， PAF-70 could not be dissolved or decomposed in almost all common solvents， which demonstrated its high chemical stability. Noteworthily， the amine group in the monomer had no negative influence on the synthetic strategy， and the amine-tagged PAF with mesopores could be obtained by the same synthetic strategy. Then using a post-synthesis modification strategy， the thiourea unit was easily introduced into the pores of PAF-70 to synthesize PAF-70-thiourea. The catalytic performance of PAF-70- thiourea was further tested using a series of alcohols in the catalysis of N-bromosuccinimide（NBS）-mediated oxidation of alcohols. In the current catalyst system PAF-70-thiourea showed high catalytic activity， high stability as well as broad substrate suitability. In comparison with the thiourea-containing MOF（IRMOF-3-thiourea） in the same catalyst system， the experimental results further demonstrated that PAFs are more suitable platforms for immobilization of catalyst for organocatalysis.



Polymer Chemistry

Synthesis of Aluminum Nanoparticles@Polymer Core-shell Nanostructures by Surface-initiated Polymerization

TAO Xingfu, HAN Chenglong, YANG Yang, LIU Kun

2022, 43(10):  20220367.  doi:10.7503/cjcu20220367

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Core-shell structured aluminum nanoparticles（Al NPs） grafted with poly（methyl methacrylate）（PMMA） were successfully prepared by the surface-initiated atom transfer radical polymerization of methyl methacrylate（MMA）. The Al NPs were modified by the surface initiator which was synthesized by the condensation reaction between （3-aminopropyl） trimethoxysilane and α-bromoisobutyryl bromide. The initiator was bonded to the Al NPs surface by the reaction of hydrolysable group of the organosilane with hydroxyl of alumina and initiated the atom transfer radical polymerization of MMA. Fourier transform infrared spectroscopy（FTIR） and ¹H nuclear magnetic resonance（¹H NMR） spectra confirmed the successfully grafting of initiator and PMMA on the surface of Al NPs. Transmission electron microscopy（TEM） images showed that Al NPs were completely coated by a uniform polymer shell with a thickness of about 15 nm. Moreover， dynamic light scattering（DLS） was used to further reveal the effect of polymerization time and the monomer concentration on the hydrodynamic diameter（D_h） of Al NP@PMMA core-shell structures. The D_hof Al NP@PMMA can be remarkably elevated by the extension of polymerization time or increase of monomer concentration.



Regulation of Silanes as External Electron Donors on Propylene/butene Sequential Polymerization

ZHOU Chengsi, ZHAO Yuanjin, HAN Meichen, YANG Xia, LIU Chenguang, HE Aihua

2022, 43(10):  20220290.  doi:10.7503/cjcu20220290

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The influences of four kinds of silanes as external electron donor（ED） with different structure and electron density［dimethyl dimethoxysilane（D1）， dibutyl dimethoxysilane（D2）， diphenyl dimethoxysilane（D3）， dicyclopentyl dimethoxysilane（D4）］ on propylene homopolymerization and propylene（first stage）-butene（second stage） sequential polymerization were investigated. The results showed that ED had significant effects on the catalytic activity， number of active centers｛［C^*］/［Ti］｝ and the stereoregularity of active centers in olefin polymerization. Density functional theory（DFT） simulations showed that with the increase in steric hindrance and electron density of ED， the adsorption energy of ED on the surface of MgCl₂ decreased， so the adsorption stability decreased. The increase in steric hindrance and electron density of ED was conducive improving the stereoregularity of the active centers. When n（D4）/n（Ti）=20， the content of isotactic polypropylene（iPP） fractions in polypropoylene（PP） reached as high as 92.8%. When n（ED）/n（Ti）=15， the rate constant for chain propagation of propylene polymerization reached the maximum value. The ED with greater steric hindrance and electron density enabled the active center of the sequential polymerization of propylene-butene with greater stereoregularity， ED had more significant effect on the polymerization activity of butene（second stage） and the melting point of the isotactic polybutene（iPB） fractions in polypropylene/polybutene alloys（PBA）.



Synthesis and Characterization of Stereoregular and Discrete Oligo（cyclohexene carbonate）s

SUN Xingyu, LUO Jing, WANG Xiadi, ZHU Qing, ZHOU Hui, LYU Xiaobing

2022, 43(10):  20220204.  doi:10.7503/cjcu20220204

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（R，R）/（S，S）-cyclohexene-1，2-diols were used as starting materials to synthesize various isotactic and syndiotactic model compounds（oligomers with 2—12 degrees of polymerization） of poly（cyclohexene carbonate）（PCHC） through an iterative coupling method using two orthogonal protecting groups and acrylation reagents. These stereoregular oligomers were characterized by high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy. The stereoregularity of PCHC can be accurately calculated by comparing the integral area of each peak in the carbonyl carbon regions of the ¹³C nuclear magnetic resonance spectrum.



Preparation of Silver-loaded Polyvinyl Alcohol Sponge and Its Interfacial Photothermal Driven Water Evaporation Performance

YANG Zhaohua, CHENG Hongjing, YANG Yi, LIU Hui, DU Feipeng, ZHANG Yunfei

2022, 43(10):  20220181.  doi:10.7503/cjcu20220181

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The utilization of photothermal materials to evaporate water under solar energy is a critical green and environmental protection technology for addressing the scarcity of freshwater resources， but its popularity and application are limited by factors such as preparation cost， evaporation efficiency， and heat loss of photothermal materials. Here， silver nanoparticles loaded polyvinyl alcohol sponge（AgNPs/PVA） solar interface evaporator was prepared by one-pot method， and the effect of AgNPs content on the photothermal performance of AgNPs/PVA in solar-driven water evaporation was investigated. The synthesized AgNPs/PVA exhibited the optimum evaporation rate under 1 kW/m ² sunlight intensity when the mass of AgNPs was 10% that of PVA， according to the results. Water may evaporate at a rate of 1.62 kg?m ^?2?h ^?1， which is 3.9 times that of pure water（0.42 kg?m ^?2?h ^?1）. The prepared AgNPs/PVA showed potential application in the field of solar driven-water evaporation due to the simple preparation process， outstanding hydrophilicity and strong evaporation performance.



Synthesis and Properties of UV/Vis-LED Excitable Photoinitiators Based on Coumarin Pyridinium Salt

LI Lun, ZHANG Jingyan, LUO Jing, LIU Ren, ZHU Yi

2022, 43(10):  20220178.  doi:10.7503/cjcu20220178

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Three novel pyridinium salt photoinitiators（PIs）， which can be excited by ultraviolet/visible light emitting diode（UV/Vis-LED）， based on coumarin framework were designed and synthesized， and their structure- activity relationship and photoinitiation activities as one-component radical photocuring initiators in acrylate system were studied. UV-Vis absorption spectra showed that the three PIs have strong absorption in the region of 300—400 nm. The steady-state photolysis and photopolymerization kinetics of three PIs were studied under the irradiation of LED@365 nm and LED@405 nm light sources. The results indicated that the three PIs all demonstrate good photolysis rate and excellent initiation activity for acrylates. Through the study of structure-activity relationship， it is found that when the electron-pushing methoxy group is introduced into the para-position of the pyridine ring， the activity of initiating the polymerization of acrylate monomers will decrease； meanwhile， the activity will increase while the electron-withdrawing acetyl group is introduced into the para-position of the pyridine ring. Differential scanning calorimetry（DSC） experiments indicated that the three pyridinium onium salt photoinitiators all demonstrate excellent thermal stability. It is interesting that when PIs were mixed with acrylic monomers， the thermal stability of the system can be improved. The generation of active species was proved by electron spin resonance（ESR） and the initiation mechanism of the initiator was discussed.



Dissipative Particle Dynamics Simulation of the Effect of Polymer Chain Rigidity on Membranes Formation by Nonsolvent Induced Phase Separation Process

TANG Yuanhui, LI Chunyu, LIN Yakai, ZHANG Chunhui, LIU Ze, YU Lixin, WANG Haihui, WANG Xiaolin

2022, 43(10):  20220169.  doi:10.7503/cjcu20220169

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In this work， a new harmonic force field that was consistent with polyethersulfone（PES） structure was constructed by a mapping between the molecular dynamics（MD） simulation and the dissipative particle dynamics（DPD）， and the effect of polymer chain rigidity on the formation of PES membranes via the nonsolvent induced phase separation（NIPS） process with N-methyl-2-pyrrolidone（NMP） as the solvent and H₂O as the nonsolvent coagulant was investigated. The results showed that the rapid exchange of the solvent and nonsolvent at the interface between NMP/PES solution and H₂O caused the accumulation of PES at the interface， resulting in the formation of a thin but dense polymer layer near the interface. And in the interior region of the PES solution， the addition of the nonsolvent induced a spinodal decomposition of the PES solution， thus presenting asymmetric morphologies with a dense layer on the top surface and a porous sub-layer beneath the top surface. Also， the enhancement of PES chain rigidity can significantly improve the phase separation speed of the system and lead to the formation of the surface layer with a smaller pore size more quickly. Moreover， the effect of PES chain rigidity on membrane structure is obviously on the surface layer rather than the sub-layer. In addition， by comparing the influence of polymer concentration on the NIPS process in different force fields， it can be found that the enhancement of PES chain rigidity with different PES concentrations did not cause fundamental changes in the characteristics and evolution trend of the phase separation process. And the effect of the harmonic force field and classical spring force field on the NIPS process is similar. The simulation results reveal that the harmonic force field constructed in this study can obviously improve the rigidity of the PES chain， and thus can be helpful to simulate the membrane formation process of phase separation more realistically.