【综述与专论】
非均相臭氧催化氧化技术处理有机废水研究进展
朱明新*, 苑斯文, 刘家扬, 潘顺龙, 周华*
（南京工业大学 环境科学与工程学院，江苏 南京 211816）
摘要：有机废水是以有机污染物为主的废水,其极易造成水质富营养化,对环境危害大。处理有机废水的方法主要有吸附法 、混凝法、芬顿氧化法、膜生物反应法和臭氧氧化法。臭氧催化氧化法主要通过在臭氧氧化体系中加入催化剂，可促进臭氧在水中的自分解，增加水中产生的羟基自由基浓度，从而提高臭氧氧化降解有机物的能力和效率。该方法由于条件可控，成本低廉，处置效率高等优点在有机废水处置领域具有广阔的应用前景。基于此，本文系统阐述了多种处理有机废水的技术方法以及臭氧催化氧化技术的研究概况，并且着重介绍了非均相臭氧催化氧化催化剂的研究进展。该研究为有机废水的高效处置提供一定的研究基础。
关键词：有机废水；非均相臭氧催化氧化；催化剂；难降解；羟基自由基
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2024）03-0001-07
DOI：10.13822/j.cnki.hxsj.2023.0630
Research Progress on Treatment of Organic Wastewater Using Heterogeneous Ozone Catalytic Oxidation Technology Zhu Ming-xin*, Yuan Si-wen, Liu Jia-yang, Pan Shun-long, Zhou Hua* (School of Environmental Science and Engineering, Nanjing Tech University, Nanjing 211816, China)
Abstract: Organic wastewater is one kind of organic pollutant-dominated wastewater, which is a major contributor to water quality eutrophication and can cause significant harm to the environment. The main methods of treating organic wastewater include adsorption, coagulation, Fenton oxidation, membrane biological reaction, and ozone oxidation. The ozone catalytic oxidation method is mainly conducted by adding a catalyst to the ozonation system, which can promote the self-decomposition of ozone and increase the concentration of hydroxyl radical produced in water, therefore the ability and efficiency of ozonation to degrade organic matter can be enhanced. This strategy has broad application prospects in the field of organic wastewater treatment due to the advantages of controllable conditions, low costs, and high disposal efficiency. This work focuses on the research of heterogeneous ozone-catalyzed oxidation catalysts that are applicable for the treatment of organic wastewater technology and ozone-catalyzed oxidation technology. It provides a certain research basis for the efficient disposal of organic wastewater.
Key words: organic wastewater; heterogeneous catalytic ozonation; catalyst; refractory; hydroxyl radicals
引用本文：朱明新, 苑斯文, 刘家扬, 等. 非均相臭氧催化氧化技术处理有机废水研究进展[J]. 化学试剂, 2024, 46(3): 1-7.
纳米零价铁的合成与修饰研究进展
肖禹圣1a，常言言1a，赵孟雅1a，田璐1a，李钠1b，赵幻希*1a，修洋*1a
(1. 长春中医药大学 a.吉林省人参科学研究院；b. 药学院，吉林 长春 130117)
摘要：纳米零价铁（Nanoscale Zero-Valent Iron，nZVI）是粒径在1～100 nm左右的零价铁粒子，具有良好的吸附性和还原性，在水体污染治理领域具有良好的应用潜力。nZVI的磁性和高表面能导致其易于团聚和钝化，降低比表面积和反应位点数量。为了提高nZVI的结构稳定性和反应活性，目前已开发了多种nZVI的合成和修饰方法。本文总结了近年来报道的nZVI的主要合成方法，包括物理合成法、化学合成法、生物合成法，以及表面修饰、负载、金属修饰、硫化修饰、乳化修饰和微生物联用等修饰方法，总结了各种方法的特点和优势，展望了nZVI的合成与修饰方法的发展方向，以期为今后nZVI的高效制备和水污染治理领域的广泛应用提供参考。
关键词：关纳米零价铁；nZVI；合成；修饰；水污染物处理
中图分类号：X703 文献标识码：A 文章编号：0258-3283（2024）03-0008-08
DOI：10.13822/j.cnki.hxsj.2023.0663
Progress in Synthesis and Modification of Nanoscale Zero-Valent Iron XIAO Yu-sheng1a, Chang Yan-yan1a, ZHAO Meng-ya1a, TIAN Lu1a, Li Na1b, ZHAO Huan-xi*1a, XIU Yang*1a (1a. Jilin Ginseng Academy, 1b. College of Pharmacy, Changchun University of Chinese Medicine, Changchun 130117, China)
Abstract: Nanoscale zero-valent iron (nZVI) refers to zero-valent iron particles with a size range of 1-100 nm. It exhibits excellent adsorption and reduction properties, making it good applicability in the field of water pollution treatment. The magnetic and high surface energy of nZVI can lead to aggregation and passivation, leading to the decrease of specific surface area and density of reactive sites. To enhance the structural stability and reactivity of nZVI, various synthesis and modification methods have been developed. This article provides a comprehensive summary of the main synthesis methods reported in recent years, including physical synthesis methods, chemical synthesis methods, and bio-synthesis methods. It also discusses various modification methods, such as surface modification, loading, metal modification, sulfidation modification, emulsion modification, and microbial association modification. The characteristics and advantages of each synthesis and modification method are described in detail. Additionally, an outlook on the future development direction of synthesis and modification methods for nZVI is provided, aiming to serve as a reference for the efficient preparation and widespread application of nZVI in water pollution treatment.
Key words：Nanoscale Zero-Valent Iron(nZVI); synthesis; modification; water pollution treatment;stabbility
引用本文：肖禹圣，常言言，赵孟雅，等. 纳米零价铁的合成与修饰研究进展[J]. 化学试剂, 2024, 46(3):8-15.
【生化与药用试剂】
香草醛异噁唑衍生物的设计合成及杀菌活性
刘伟童，朱长恒，蒋禹，赵汗青*
（北京农学院 农业农村部华北都市农业重点实验室 北京 102206）
摘要：为了寻找结构新颖、杀菌活性更好的绿色农药。选用天然产物香草醛作为基本原料，引入五元杂环异噁唑结构，首次设计并合成了28个香草醛异噁唑类衍生物。结构经核磁共振氢谱、碳谱及高分辨质谱分析确认。测试了所有目标衍生物对烟草灰霉病菌[Botrytis cinerea]、层出镰刀菌[Fusarium proliferatum]、木贼镰刀菌[Fusarium equiseti]、玉米圆斑病菌[Bipolaris zeicola]、胶胞炭疽菌[Colletotrichum gloeosporioides]、草茎点霉菌[Phoma herbarum]6种广谱菌的杀菌活性。杀菌活性测定结果显示：在50µg/mL质量浓度下，部分化合物对6种真菌的菌丝生长均具有一定抑制作用，2-甲氧基-4-(5-苯基异噁唑-3-基)苯乙酸酯对6种真菌的抑菌活性整体良好，对玉米圆斑病菌等3种菌的抑菌活性超过对照组百菌清；2-甲氧基-4-(5-(4-乙基苯基)异噁唑-3-基)苯酚对烟草灰霉病菌的抑菌活性最高，抑菌率可以达到93%。初步构效关系表明，对活性片段香草醛上的酚羟基进行乙酰化衍生，有助于提高化合物对6种病原菌的抑菌活性，为后续的生物活性研究提供了参考。
关键词：香草醛；异噁唑；合成；百菌清；杀菌活性
中图分类号：R9 文献标识码：A 文章编号：0258-3283（2024）03-0016-08
DOI：10.13822/j.cnki.hxsj.2023.0677
Design, Synthesis and Biological Activity of Vanillin Isoxazole Derivative LIU Wei-tong, ZHU Chang-heng, JIANG Yu, ZHAO Han-qing* (Key Laboratory of Urban Agriculture (North China), Ministry of Agriculture, Beijing University Of Agriculture, Beijing 102206, China)
Abstract: In order to develop green pesticides with novel structure and better antifungal activity. The natural product vanillin was selected as the basic material, and a five-membered isoxazole was introduced into its structure. 28 vanillin isoxazole derivatives were designed and synthesized. Their compounds were confirmed by 1H NMR, 13C NMR and HRMS. Their antifungal activities against Botrytis cinerea, Fusarium proliferatum, Fusarium equiseti, Bipolaris zeicola, Colletotrichum gloeosporioides and Phoma herbarum were evaluated. The antifungal activity study indicated that at a mass concentration of 50 µg/mL, some compounds had certain inhibitory effects on the mycelial growth of six fungi. The antifungal activity of target compound 4b against six fungi was good as a whole. Compound 4b against three kinds of bacteria, such as Bipolaris zeicola, was higher than that of the control group chlorothalonil. Moreover, the target compound 3f had the highest antifungal activity against Botrytis cinerea, and the antifungal rate can reach 93%. The preliminary structure-activity relationship showed that acetylation and derivatization of phenolic hydroxyl groups on vanillin were helpful to improve the antifungal activity of the compound against six fungi, and provided a reference for the subsequent biological activity research.
Keywords: vanillin; isoxazole; synthesis; antifungal activity
引用本文：刘伟童，朱长恒，蒋禹，等. 香草醛异噁唑衍生物的设计合成及杀菌活性[J]. 化学试剂，2024, 46(3)：16-23.
1,3,4-噁二唑类化合物的合成及生物活性研究进展
杨碧蓉1，邰晔弘1，王玉梨1，王顺优1，张海珍2，杨岚*1
（1．贵州大学 a. 药学院；b．贵州省合成药物工程实验室，贵州 贵阳 550025；
2. 贵州省联大检测技术有限公司， 贵州 贵阳 550025）
摘要：1,3,4-噁二唑类化合物是一类重要的含氮五元芳香杂环类结构单元，可与多种药效团融合，产生不同的生物活性，因此引起了人们的关注，也显示了广泛的应用和发展前景，在医药和农药领域尤为突出。综述了国内外以酰肼环合法、Huisgen反应高效构建1,3,4-噁二唑类化合物的方法，同时对1,3,4-噁二唑类化合物在抗病毒、抗菌、抗肿瘤、除草、杀虫等方面的生物活性进行了介绍，并对各类化合物的构效关系进行总结，为进一步研究1,3,4-噁二唑类化合物的设计合成及其生物活性提供参考和借鉴。
关键词：1,3,4- 噁二唑；合成；药效团融合；生物活性；研究进展
中图分类号：O626.24 文献标识码：A 文章编号：0258-3283（2024）03-0024-09
DOI：10.13822/j.cnki.hxsj.2023.0595
Research Progress in the Syntheses and Biological Activities of 1,3,4-Oxadiazole YANG Bi-rong1, TAI Ye-hong1, WANG Yu-li1, WANG Shun-you1, ZHANG Hai-zhen2, YANG Lan*1 (1a. College of Pharmacy, 1b. Engineering Laboratory for Synthetic Drugs, Guiyang 550025, China; 2. Guizhou Lianda Testing Technology Co. Ltd., Guiyang 550025, China)
Abstract: 1,3,4-oxadiazoles are important class of nitrogen-containing five-membered aromatic heterocyclic structural unit, which can produce a variety of biological activities after combing with multi kinds of pharmacophore, so many compounds containing 1,3,4-oxadiazoles core structure have attracted people’s attention and show a wide application and development prospects, especially in the field of medicine and agriculture.The efficient construction of 1,3,4-oxadiazole compounds by hydrazide ring method and Huisgen reaction,meanwhile,the biologicl activities of 1,3,4-oxadiazole such asantiviral,antibacterial,antitumor,herbicidal and insecticidal and so on have been introduced,and summarized the structure-activity relationship of various compounds.It provides reference and guidance for further study on the design,synthesis and biological activities of 1,3,4-oxadiazole compounds.
Keywords：1,3,4-oxadiazole; synthesis; pharmacophore-merging; biological activity; research progress
引用本文：杨碧蓉, 邰晔弘, 王玉梨, 等. 1,3,4-噁二唑类化合物的合成及生物活性研究进展[J].化学试剂, 2024,46(3):24-32.
【功能材料】
甲醇对于PEI-SBA固态胺制备及其性能的影响
胡海涛1,2，郑岳青*1，林贻超*2
（1. 宁波大学 材料科学与化学工程学院，浙江 宁波 ，315211；2. 中国科学院宁波材料技术与工程研究所，浙江省先进燃料电池与电解池技术重点实验室，浙江 宁波 315201）
摘要：固态胺材料具有优异的二氧化碳（CO2）选择吸附性能，是一类潜在的CO2捕集材料。作为一种重要的固态胺材料，SBA-15负载聚乙烯亚胺（PEI-SBA-15）由于原材料较为廉价且性能优异受到了大量的关注。PEI-SBA-15的制备过程需要采用甲醇溶剂，而溶剂使用量对于其CO2吸附性能的影响尚无系统研究。系统研究了溶剂使用量对SBA-15负载聚乙烯亚胺的CO2吸附性能的影响。研究结果表明，可以同时实现提升CO2吸附性能和CO2/N2选择性和大幅降低甲醇的使用量。本研究工作对于降低PEI-SBA-15的制备成本以及提升制备过程环保性具有重要意义。
关键词：SBA-15分子筛；CO2吸附；固态胺；聚乙烯亚胺；溶剂作用
中图分类号：TQ-9 文献标识码：A 文章编号：0258-3283（2024）03-0033-06
DOI：10.13822/j.cnki.hxsj.2023.0717
Effect of Methanol on the Preparation and Performance of PEI-SBA Solid Amine HU Hai-tao1,2, ZHENG Yue-qing*1, LIN Yi-chao*2 (1. School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China; 2. Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China)
Abstract: Solid amine materials have excellent carbon dioxide (CO2) selective adsorption properties and are potential materials for CO2 capture. As an important type of solid amine material, polyethyleneimine-loaded SBA-15 (PEI-SBA-15) has attracted a lot of attention due to its relatively low cost of raw materials and excellent performance. The preparation process of PEI-SBA-15 requires the use of methanol as a solvent, but the influence of solvent usage on its CO2 adsorption performance has not been systematically studied. Given this, this work systematically investigates the effect of solvent usage on the CO2 adsorption performance of SBA-15 loaded with polyethyleneimine. The research results show that it is possible to simultaneously improve CO2 adsorption performance, and CO2/N2 selectivity, and significantly reduce the usage of methanol. This research work is of great significance for reducing the preparation cost of PEI-SBA-15 and improving the environmental friendliness of the preparation process.
Keywords: SBA-15 molecular sieve; CO2 adsorption; solid amine; polyethyleneimine ; solvent effect;carbon neutrality
引用本文：胡海涛，郑岳青，林贻超. 甲醇对于PEI-SBA固态胺制备及其性能的影响[J]. 化学试剂，2024, 46（3）：33-38.
La(OH)3/SiO2气凝胶的制备及其在净化含磷废水中的应用
林晓燕1，练钊华1,2，林璟1，左建良1，刘自力*1
(1. 广州大学 化学化工学院，广东 广州 510006；2. 广西壮族自治区梧州市龙圩区政贤路78号，广西 梧州 543000)
摘要：采用浸渍沉淀法，制备了La(OH)3/SiO2气凝胶吸附材料，并利用XRD、SEM、FTIR、XPS、BET对吸附剂结构、表面形貌等进行表征。研究了吸附剂投加量、初始pH和共存离子对磷酸根吸附效果的影响，探究了吸附过程的吸附动力学、等温吸附过程及吸附热力学模型。实验结果表明：AER-La0.2（质量比为0.2:1时）的磷酸根吸附量可达294.1 mg/g (La)；且对磷酸根具有较好的吸附选择性；吸附剂添加量为0.4 g/L时获得最好的吸附能力；在较宽的pH范围内保持了较好的吸附能力。准二级动力学模型和Langmuir等温吸附模型的结果更准确，说明吸附过程主要受化学吸附控制且主要为单层吸附。吸附热力学的结果表明，吸附过程为吸热过程，温度越高对吸附越有利。结合表征手段，推断AER-La0.2的主要吸附作用可能为静电吸引及配体交换。
关键词：La(OH)3；气凝胶；吸附；磷酸根；机理
中图分类号：TQ13 文献标识码：A 文章编号：0258-3283（2024）03-0039-10
DOI：10.13822/j.cnki.hxsj.2023.0634
Preparation of La(OH)3/ SiO2 Aerogel and Its Application in the Purification of Phosphorus Containing Wastewater LIN Xiao-yan1, LIAN Zhao-hua1,2, LIN Jing1, ZUO Jian-liang1, LIU Zi-li*1 (1. School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China; 2. No. 78, Zhengxian Road, Longwei District, Wuzhou City, Guangxi Zhuang Autonomous Region, Wuzhou 543000, China)
Abstract: La(OH)3/SiO2 aerogel adsorption materials were prepared via immersion precipitation technique and the adsorbent structure and surface morphology were characterized by XRD, SEM, FTIR, XPS, and BET. The effects of adsorbent dosage, initial pH values, and coexisting ions on the adsorption effect of phosphate were investigated. Meanwhile, the adsorption kinetics, isothermal adsorption processes, and adsorption thermodynamic models were studied. Experimental results showed that the phosphate adsorption capacity of AER-La0.2 (at a mass ratio of 0.2:1) was up to 294.1 mg/g (La) with good adsorption selectivity. The best adsorption capacity was obtained at an adsorbent addition of 0.4 g/L, and very good adsorption capacity can be maintained in a wide pH range. As a fact the quasi-second-order kinetic model and the Langmuir isothermal adsorption model fit better with the actual data, it was indicated that the adsorption process was mainly controlled by chemisorption and monolayer adsorption. The results of adsorption thermodynamics showed that the adsorption process is heat-absorbing, and higher temperature is more favorable for adsorption. Combined with the characterization methods, it is inferred that the main adsorption of AER-La0.2 may be through electrostatic attraction and ligand exchange.
Key words: lanthanum hydroxide; aerogel; adsorption; phosphate; mechanism
引用本文：林晓燕, 练钊华,林璟, 等.La(OH)3/SiO2气凝胶的制备及其在净化含磷废水中的应用[J]. 化学试剂，2024，46(3)：39-48.
CdS/Nb2O5异质结材料的制备、表征及光催化降解
环丙沙星研究
陈玲霞，朱蓓蓓，李百裕，周杰*
(南通职业大学 药品与环境工程学院，江苏 南通 226007)
摘要：采用水热法制备了CdS/Nb2O5纳米复合材料，利用X-射线衍射光谱（XRD）、透射电镜（TEM）、红外光谱（FT-IR）、X-射线光电子能谱（XPS）和紫外-可见漫反射（UV-vis DRS）对制备的材料进行表征。通过可见光下降解环丙沙星评价材料的光催化活性。结果表明，制备的CdS/Nb2O5纳米复合材料由CdS纳米颗粒分散于Nb2O5纳米笼表面，二者形成紧密的II型异质结；CdS的引入增强了Nb2O5的可见光吸收性能，同时提高了光生载流子的分离效率；当CdS的含量为15%时，CdS/Nb2O5可在60 min实现环丙沙星的高效降解，其反应速率常数是CdS的7.5倍，Nb2O5的20倍，空穴是该降解反应的主要活性物种，研究结果为抗生素废水的高效治理提供了一条新思路。
关键词：CdS；Nb2O5；异质结；光催化；环丙沙星
中图分类号：O643.36 文献标识码：A 文章编号：0258-3283（2024）03-0049-07
DOI：10.13822/j.cnki.hxsj.2023.0751
Synthesis, characterization, and photocatalytic degradation of ciprofloxacin using CdS/Nb2O5 heterojunction materials CHEN Ling-xia, ZHU Bei-bei, LI Bai-yu, Zhou Jie* (College of Pharmaceutical and Environmental Engineering, Nantong Vocational University, Nantong 226007, China)
Abstract: CdS/Nb2O5 nanocomposites were prepared using a hydrothermal method, and the prepared materials were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS). The photocatalytic activity of the material was evaluated by the degradation of ciprofloxacin under visible light eradiation. The results showed that the prepared CdS/Nb2O5 nanocomposites consisted of dispersed CdS nanoparticles on the surface of Nb2O5 nanocages, forming a closely packed type II heterojunction. The introduction of CdS enhanced the visible light absorption of Nb2O5 and improved the separation efficiency of photo-generated charge carriers. When the content of CdS was 15%, the CdS/Nb2O5 achieved efficient degradation of ciprofloxacin within 60 minutes, with a reaction rate constant 7.5 times larger than that of CdS and 20 times larger than that of Nb2O5, indicating that photo-generated holes were the main active species in the degradation reaction. This study provides a new approach for the efficient treatment of antibiotic wastewater.
Key words: CdS; Nb2O5; heterojunction; photocatalysis; ciprofloxacin
引用本文：陈玲霞，朱蓓蓓，李百裕，等. CdS/Nb2O5异质结材料的制备、表征及光催化降解环丙沙星研究[J]. 化学试剂, 2024, 46(3):49-55.
【分离提取技术】
肉桂子化学成分鉴定、总黄酮提取工艺优化及其抗氧化活性研究
黄梦a,b，刘宏炳a,b，杨珍a,b，燕雪花*a,b
（新疆医科大学 a. 中医学院，b. 新疆名医名方与特色方剂学重点实验室 新疆 乌鲁木齐 830017）
摘要：本研究采用超高效液相色谱串联质谱法（UHPLC-MS/MS）鉴定肉桂子有效成分；基于单因素实验，采用响应面法优化肉桂子总黄酮提取工艺及含量测定；通过DPPH法、铁离子还原能力法评价其体外抗氧化活性。结果表明：肉桂子鉴定出135个有效成分；总黄酮最佳提取工艺为乙醇体积分数42%、料液比1:36（g/mL）、功率350 W、超声时长43 min，在此条件下，总黄酮含量为377.90 mg/mL；S4总黄酮含量最高，S18总黄酮含量最低；总黄酮对DPPH·和Fe3+·均表现出较好的清除能力。综上，肉桂子含有黄酮类、萜类、酚类、生物碱等多种成分，该总黄酮提取工艺合理，不同批次肉桂子总黄酮均有一定的抗氧化作用。
关键词：肉桂子；超高效液相色谱-串联质谱法；响应面；总黄酮；抗氧化
中图分类号：TQ461 文献标识码：A 文章编号：0258-3283（2024）03-0056-10
DOI：10.13822/j.cnki.hxsj.2023.0699
Identification of Chemical Constituents, Optimization of Total Flavonoids Extraction Process, and Study on Antioxidant Activity of Fructus Cinnamomi cassiae immaturi HUANG Meng, LIU Hong-bing, YANG Zhen, YAN Xue-hua*(a. College of traditional Chinese medicine; b. Key Laboratory of Famous Medical Formulas and Characteristic Prescriptions in Xinjiang, Xinjiang Medical University, Urumqi 830017, China)
Abstract: This study utilized ultrahigh performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) to identify the effective components of Fructus Cinnamomi cassiae immaturi. Based on single factor experiments, response surface methodology was used to optimize the extraction process of total flavonoids from Fructus Cinnamomi cassiae immaturi. Based on this extraction process, the content of total flavonoids was determined. Its in vitro antioxidant activity was evaluated through DPPH method and iron ion reduction ability method. The results showed that 135 effective components were identified from Fructus Cinnamomi cassiae immaturi. The optimal extraction conditions were as follows: ethanol volume fraction of 42%, solid-liquid ratio of 1:36 (g/mL), power of 350 W, and extraction time of 43 minutes. Under these conditions, the total flavonoid content is 377.90 mg/mL. It was found that S4 has the highest total flavonoid content, while S18 has the lowest total flavonoid content, and total flavonoids showed good scavenging ability for both DPPH and Fe3+. In summary, the compounds of Fructus Cinnamomi cassiae immaturi consist of flavonoids, terpenoids, phenols, alkaloids, etc. The extraction process of total flavonoids is reasonably designed, and total flavonoids of different batches of Fructus Cinnamomi cassiae immaturi have certain antioxidant effects.
Key words: Fructus Cinnamomi cassiae immaturi; ultrahigh performance liquid chromatography tandem mass spectrometry; response surface; total flavonoids; antioxidant
引用本文：黄梦，刘宏炳，杨珍，等. 肉桂子化学成分鉴定、总黄酮提取工艺优化及其抗氧化活性研究[J]. 化学试剂，2024,46(3)：56-65.
【电化学和新能源】
用于锂离子电池高压LNMO正极的瓜尔胶-木聚糖粘结剂
胡钰珺1，慎洋1，韦健伦1，邓媛1，杨斐婷1，杨雅姿1，苏静*1,2
（1. 广西大学 化学化工学院，广西 南宁 530004；2. 广西高校应用化学技术与资源开发重点实验室，广西 南宁 530004）
摘要：具有尖晶石结构的镍锰酸锂（LNMO）被认为是最具有前景的正极材料之一，然而高工作电压会严重影响LNMO正极的循环寿命，导致在充放电过程中容量快速衰减、循环性能较差。针对锂离子电池无钴正极材料镍锰酸锂（LNMO）在高电压下的界面不稳定的缺点，开发了适用于5.0V高压LNMO正极的木聚糖-瓜尔胶复合粘结剂。研究结果表明，瓜尔胶与木聚糖通过交联形成酯基，使粘结剂具备良好的机械性能；与PVDF粘结剂相比，使用复合粘结剂的LNMO的循环稳定性得到了显著提高，是具有应用前景的锂离子电池高压正极粘结剂。
关键词：瓜尔胶；木聚糖；镍锰酸锂；锂离子电池；粘结剂
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）03-0066-07
DOI：10.13822/j.cnki.hxsj.2023.0721
Guar Gum-Xylan Binder for High-Voltage LNMO Cathode of Lithium-ion Battery HU Yu-jun1, SHEN Yang1, WEI Jian-lun1, DENG Yuan1, YANG Fei-ting1, YANG Ya-zi1, SU Jing*1,2 (1. School of Chemistry and Chemical Engineering, Nanning 530004, China; 2. Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development, Nanning 530004, China)
Abstract：Lithium nickel manganese oxide (LNMO) with spinel structure is considered to be one of the most promising cathode materials,but the high working voltage will seriously affect the cycle life of the LNMO cathode,resulting in rapid capacity decay and poor cycle performance during charging and discharging.In order to solve the shortcomings of the interface instability of LNMO,a coblt-free acthode material for lithium-ion battery,at high voltage,a xylan-guar gum composite binder suitable for 5.0 V high-voltage LNMO cathode was developed.The results showed that guar gum and xylan formed an ester group via crosslinking,which grafted the binder with good mechanical properties.Compared with PVDF binder,the cycle stability of LNMO with composite binder has been significantly improved,which is a promising binder for the high-voltage cathode of lithium-ion battery.
Key words: guar gum; xylan; LNMO; lithium-ion battery; binder
引用本文：胡钰珺，慎洋，韦健伦，等. 用于锂离子电池高压LNMO正极的瓜尔胶-木聚糖粘结剂[J]. 化学试剂, 2024, 46(3): 66-72.
【化学品与环境】
食药两用物质天麻、灵芝的外源性污染物分析
黄小兰，谭春蓉，朱德文，易良键，郑容*
(重庆市万州食品药品检验所，三峡库区道地药材开发利用重庆市重点实验室 重庆 404100)
摘要：测定食药两用物质天麻、灵芝的外源性污染物，进行安全性风险评估。采用酸碱滴定法测定二氧化硫残留量，微波消解-电感耦合等离子体质谱法测定7种重金属铬、铜、砷、镉、铅、汞和钡含量，气相色谱质谱联用法测定44种农药残留量，并利用内梅罗综合污染指数法评价重金属污染情况。15批天麻样品中二氧化硫检出率100%，超标率100%，25批灵芝样品检出率12%，无超标现象。天麻和灵芝中重金属含量按中药材属性判定时，合格率100%，按食品属性参照国家安全食品标准判定时，15批天麻中Cr超标11批，25批灵芝样品中Pb超标1批，As超标2批，Cr超标14批；内梅罗综合污染指数显示，天麻和灵芝中轻度以上污染率为73%和40%。灵芝中共检出毒死蜱、联苯菊酯和百菌清3种农药，均符合相关限量要求，天麻样品未检出农药。天麻和灵芝均存在外源性污染风险，天麻中二氧化硫和重金属超标，灵芝有农药超标的风险，研究可为食药两用类物质开展安全性风险评估及制定限量标准提供参考和依据。
关键词：天麻；灵芝；二氧化硫残留量；重金属；农药残留量；电感耦合等离子体质谱仪；气相色谱质谱联用仪
中图分类号：R282.71 文献标识码：A 文章编号：0258-3283（2024）03-0073-08
DOI：10.13822/j.cnki.hxsj.2023.0750
Analysis of Exogenous Pollutants in Gastrodia elata B1. and Ganoderma lucidum of Medicinal and Edible Homologous Substances HUANG Xiao-lan, TAN Chun-rong, ZHU De-wen, YI Liang-jian, ZHENG Rong* （Chongqing Key Laboratory for the Development and Utilization of Authentic Medicinal Materials in the Three Gorges Reservoir Area, Chongqing Wanzhou Food and Drug Inspection Institute, Chongqing 404100, China）
Abstract: The exogenous pollutants in Gastrodia elata B1. and Ganoderma lucidum were determined for security risk assessment. The residues of sulfur dioxide were determined by acid-base titration method. Chromium, copper, arsenic, cadmium, lead, mercury and barium were determined by microwave digestion-inductively coupled plasma mass spectrometry, and evaluated by Nemerow comprehensive pollution index method. 44 kinds of pesticide residues were determined by gas chromatography-mass spectrometry. The sulfur dioxide detection rate of 15 batches of Gastrodia elata B1. samples were 100%, resulting in an excess rate of 100%. The detection rate of 25 batches of Ganoderma lucidum samples was 12%, therefore showing no exceedance phenomenon. When Gastrodia elata B1. and Ganoderma lucidum were evaluated according to the standard of Chinese medicinal materials, the qualified rate of heavy metals was 100%. If they were determined according to food standards, 15 batches of Gastrodia elata B1. exceeded Cr 11 batches, 25 batches of Ganoderma lucidum samples exceeded Pb 1 batch, As exceeded 2 batches, and Cr exceeded 14 batches. Nemero comprehensive pollution index shows that Gastrodia elata B1.and Ganoderma lucidum have mild pollution rates of 73% and 40%, respectively. Chlorpyrifos, bifenthrin, and chlorothalonil were detected in Ganoderma lucidum, all of which met the relevant limit requirements, and no pesticides were detected in Gastrodia elata B1. Gastrodia elata B1.and Ganoderma lucidum both have exogenous pollution risks, the sulfur dioxide residue, and heavy metals in Gastrodia elata B1. exceed the standard, and the risk of pesticides exceeding the standard exists in Ganoderma lucidum. This study can provide a reference and basis for the safety risk assessment and the formulation of the limit standard of drug and food homologous substances.
Key words: Gastrodia elata B1.; Ganoderma lucidum; sulfur dioxide residues; heavy metals; pesticide residues; ICP-MS; GC-MS/MS
引用本文：黄小兰[1]，谭春蓉，朱德文，等. 食药两用物质天麻、灵芝的外源性污染物分析[J]. 化学试剂, 2024, 46(3):73-80.
铁改性香蒲生物炭吸附去除水中刚果红的研究
赵卿瑞1，黄钰焜1，张洪培1,2，郭嘉欣1，王程豫1，王肖丹1,2，郑宾国*1,2
（1. 郑州航空工业管理学院 土木建筑学院 ；2. 郑州市流域环境治理重点实验室）
摘要: 以湿地植物香蒲为原料，通过热解制备了生物炭（BC），采用水热法将Fe与BC复合，制备了具有良好磁性能的铁改性生物炭（Fe-BC）。采用SEM、BET、FT-IR、XRD、XPS和VSM等，分析了Fe-BC的结构形貌特性及磁性能，并研究了Fe-BC吸附去除水中典型有机染料刚果（CR）的性能。结果表明： 制备的Fe-BC具有良好的磁性，当CR浓度为100 mg/L、Fe-BC投加量为40 mg、溶液pH为3、吸附时间90 min、反应体系温度25℃时，CR的去除率可达99.6%；此外，Cu2+、Zn2+、Mn2+金属阳离子可提高Fe-BC对CR 的去除率； Fe-BC 进行3次吸附-脱附后，Fe-BC 对水中CR仍有良好吸附性能，表明磁性Fe-BC具有良好的循环稳定性；通过对动力学模型与热力学模型的拟合，表明Fe-BC 对水中CR的吸附过程主要受化学吸附影响，且为自发不可逆的吸热反应。
关键词: 香蒲；刚果红；磁性生物炭；吸附；热力学；动力学
中图分类号：X52 文献标识码：A 文章编号：0258-3283(2024)03-0081-10
DOI：10.13822/j.cnki.hxsj.2023.0601
Adsorptive Removal of Congo Red from Water by Iron-Modified Cattail Biochar Zhao Qing-rui1, Huang Yu-kun1, Zhang Hong-pei1,2, Guo Jia-xin1, Wang Cheng-yu1, Wang Xiao-dan, Zheng Bin-guo*1,2 (1.School of Civil Engineering and Architecture, Zhengzhou University of Aeronautics, Zhengzhou 450000, China; 2. Zhengzhou Key Laboratory of Watershed Environmental Treatment, Zhengzhou 450000, China)
Abstract：Biochar (BC) was produced through the pyrolysis of cattail, a wetland plant, and iron-modified biochar (Fe-BC) with strong magnetic properties was then synthesized through hydrothermal compounding of Fe and BC. The structural morphology and magnetic properties of Fe-BC were characterized through numerous techniques such as TEM, BET, FT-IR, XRD, XPS, and VSM. Its potential for adsorbing and removing Congo (CR), a common waterborne organic dye, was evaluated. It was revealed that the Fe-BC exhibited highly effective magnetic properties, with a CR removal rate of 99.6% achieved at a CR concentration of 100 mg/L, Fe-BC dosage of 40 mg, solution pH of 3, an adsorption time of 90 minutes, and an adsorption temperature of 25℃. Notably, the removal of CR by Fe-BC can be strengthened by Cu2+, Zn2+, and Mn2+ metal cations. Moreover, the Fe-BC exhibited very stable adsorption performance for CR after three cycles of adsorption and desorption, demonstrating very good cyclic stability of the magnetic Fe-BC. The fitting of the kinetic model to the thermodynamic model suggested that the adsorption of CR onto Fe-BC is predominantly affected by chemisorption and characterized as a spontaneous, irreversible endothermic reaction.
Key words：cattail; congo red; magnetic biochar; adsorption; thermodynamic; dynamics
引用本文：赵卿瑞, 黄钰焜, 张洪培, 等. 铁改性湿地植物生物炭吸附去除水中刚果红的研究[J]. 化学试剂, 2024, 46(3):81-90 .
【分析与测试】
色谱指纹图谱聚类分析在法庭溯源领域的应用
李昊洋，张文骥*，韩祺瑞，罗颖超
(中国刑事警察学院刑事科学技术学院，辽宁 沈阳 110854)
摘要：物证化学指纹的检验在法庭溯源中至关重要。传统化学法检验耗费样品多，检出限高，检测标志物数量少；光谱分析方法虽消耗样品少、检测速度快，但是不能分离组分，易出现干扰情况。色谱能够分离分析复杂组分，适合化学指纹的检验。化学计量学、化学模式识别方法使得色谱分析方法发生了巨变，分析色谱整体数据提高了数据的利用率，增加了化学指纹的准确性。色谱指纹图谱为聚类分析提供了充足数据，聚类分析方法则充分挖掘了隐藏在色谱指纹图谱中的关键信息。该文对化学模式识别和聚类分析进行了简要介绍，系统总结了色谱指纹图谱无监督模式识别方法在法庭溯源中的应用，介绍了一些色谱新技术，并对色谱指纹图谱在法庭溯源未来发展应用提供了建议。
关键词：色谱指纹图谱；聚类分析；化学计量学；溯源分析；法庭科学
中图分类号：O65 文献标识码：A 文章编号：0258-3283（2024）03-0091-08
DOI：10.13822/j.cnki.hxsj.2023.0676
Applications of Chromatographic Fingerprint Clustering Analysis in Forensic Tracing LI Hao-yang, ZHANG Wen-ji*, HAN Qi-rui, LUO Ying-chao (Department of Forensic Science of Criminal Investigation Police University of China, Shenyang 110854, China)
Abstract: The testing of chemical fingerprints in physical evidence is crucial in forensic tracing. Traditional chemical test methods require a lot of samples, have high detection limits, and possess a small amount of detection markers. Although spectral analysis methods consume less samples and have faster detection speed, they cannot separate each component in complex samples and are susceptible to interference. Chromatography can separate and analyze complex components, making it suitable for chemical fingerprint testing. Chemometrics and chemical pattern recognition methods have brought about significant changes in chromatographic analysis methods, improving the utilization of overall chromatographic data and increasing the accuracy of determining chemical fingerprints. Chromatographic fingerprints provide sufficient information for clustering analysis while clustering analysis methods fully explore the key information hidden in chromatographic fingerprints. This review article provides a brief introduction to chemical pattern recognition and cluster analysis, systematically summarizes the applications of unsupervised pattern recognition methods for chromatographic fingerprints in court tracing, introduces some new chromatographic technologies, and additionally provides suggestions for the future development and application of chromatographic fingerprints in forensic tracing.
Key words: chromatographic fingerprint; cluster analysis; chemometrics; tracing analysis; forensic science
引用本文：李昊洋，张文骥，韩祺瑞，等. 色谱指纹图谱聚类分析在法庭溯源领域的应用[J] 化学试剂, 2024, 46(3): 91-98.
细辛、土壤中重金属含量测定及生态风险评估
姜先慧1,2，于敏*2，焦连庆2，张凤清*1
（1. 长春工业大学 化学与生命科学学院，吉林 长春 130012；2. 吉林省中医药科学院，吉林 长春 130012)
摘要：选取六片种植地的细辛及土壤作为研究对象，通过比较电感耦合等离子体-质谱法（ICP－MS）测As、Hg，全自动汞分析仪测Hg，原子荧光光度仪（AFS）测As的实验结果，确定Hg的测定采用全自动汞分析仪，As的测定采用AFS。Pb、Cd、Cu、Cr选用ICP-MS进行测定，计算细辛对重金属元素的富集系数，并对土壤中6种重金属元素进行生态风险评估。结果显示，十二批细辛除Cd外，Pb、As、Cu、Cr、Hg均符合药用植物及制剂进出口绿色行业标准；Cd实测值为2.02±0.47 mg/kg，超标程度573%，富集系数为9.14±3.24；Cr的富集系数为1.43±0.96。六片细辛种植地土壤潜在生态风险系数（Ei r）均低于40，潜在生态风险指数（RI）均低于110，属于轻微污染。Cd的土壤污染最为严重，针对Cd污染的土壤治理及修复成为迫切需要解决的问题。
关键词：细辛；土壤；重金属；富集系数；风险评估
中图分类号：X833 文献标识码：A 文章编号：0258-3283(2024)03-0099-06
DOI：10.13822/j.cnki.hxsj.2023.0656
Determination of Heavy Metal Content in Asarum and Soil and Ecological Risk Assessment JIANG Xian-hui1,2, YU Min*2, JIAO Lian-qing2, ZHANG Feng-qing*1 （1. College of Chemistry and Life Sciences, Changchun University of Technology, Jilin 130012, China; 2. Jilin Academy of Traditional Chinese Medicine, Jilin 130012, China）
Abstract: Six planting areas of Asarum and soil were selected as the research subjects. Herein, Hg was measured using an automatic mercury analyzer, and As was measured using an atomic fluorescence spectrometer (AFS), Pb, Cd, Cu, and Cr were measured using inductively coupled plasma mass spectrometry (ICP-MS). By comparing the experimental results of As and Hg measured by ICP-MS, Hg measured by automatic mercury analyzer, and As measured by AFS, the enrichment coefficients of Asarum for heavy metal elements were calculated, and ecological risk assessment was conducted on six types of heavy metal elements in the soils. Results showed that the twelve batches of Asarum all met the green industry standards for the import and export of medicinal plants and preparations except for Cd, including Pb, As, Cu, Cr, and Hg. The measured value for Cd is 2.02 ± 0.47 mg/kg, with an exceeding degree of 573% and an enrichment coefficient of 9.14 ± 3.24. The enrichment coefficient of Cr is 1.43 ± 0.96. The potential ecological risk coefficient (Ei r) of the soil in the six Asarum planting areas is all below 40, and the potential ecological risk index (RI) is all below 110, indicating a slight extent of pollution. The soil pollution caused by Cd is the most severe, therefore soil remediation and remediation for Cd pollution have become urgent issues to be addressed.
Key words：Asarum heterotropoides; soil; heavy metal; enrichment coefficient; risk assessment
引用本文：姜先慧，于敏，焦连庆，等. 细辛、土壤中重金属含量测定及生态风险评估[J]. 化学试剂，2024，46(3)：99-104.
【标准物质与标准品】
系列水分活度标准物质的研制
郑涵，王海峰*，张艾蕊，李佳
(中国计量科学研究院，北京，100029)
摘要：水分活度的准确测定对食品安全具有重要意义。水分活度仪急需水分活度标准物质进行校准。研制了氯化钠（NaCl）溶液和氯化锂（LiCl）溶液水分活度标准物质。采用质量平衡法和电位滴定法测定LiCl的纯度。采用重量法制备LiCl溶液，利用LiCl和水的质量以及LiCl纯度计算LiCl的质量摩尔浓度（m）。将m代入德拜-休克尔方程，计算得到渗透系数（ϕ）。根据物理化学基本原理，由m和ϕ计算得到水分活度的标准值。另外，还采用NaCl纯度标准物质制备了NaCl溶液水分活度标准物质，并计算出其水分活度标准值。7种标准物质的标准值分别为0.250、0.500、0.762、0.797、0.850、0.900和0 950，它们的扩展不确定度（U，k=2）不超过0.007。以德拜-休克尔方程表示的ϕ的标准数据，由美国标准局（NBS）统计并发布。该系列水分活度标准物质可用于水分活度仪的校准和水分活度测量方法的验证。
关键词：水分活度；标准物质；渗透系数；氯化钠；氯化锂；不确定度
中图分类号：O657.12 文献标识码：A 文章编号：0258-3283（2024）03-0105-07
DOI：10.13822/j.cnki.hxsj.2023.0675
Development of a Series of Certified Reference Materials of Water activity Zheng Han, WANG Hai-feng*, ZHANG Ai-rui, LI Jia (National Institute of Metrology of China, Beijing, 100029)
Abstract: Accurate determination of water activity is essential for food safety. The water activity meter needs the certified reference materials (CRMs) for water activity calibration. Here in this study, the CRMs of sodium chloride (NaCl) solution and lithium chloride (LiCl) solution for water activity were developed. The purity of LiCl was determined using the mass balance method and the potentiometric titration. The LiCl solution was prepared using the gravimetric method and its molarity (m) was calculated using the mass of LiCl and water, and the purity of LiCl. m was introduced into the Debye-Hückel equation, and then the corresponding osmotic coefficient (ϕ) was calculated. The certified value of a was calculated using ϕ and m according to physical chemistry basic theory. Furthermore, the CRMs of NaCl solution for water activity calibration were prepared using the CRM of NaCl for purity, and then their water activities were calculated. The certified values of seven CRMs were 0.250, 0.500, 0.762, 0.797, 0.850, 0.900, and 0.950, respectively. The reference value of ϕ expressed in the Debye-Hückel equation was published by the National Bureau of Standards (NBS) of the USA after the statistics and analysis. Their uncertainty (U, k=2) was less than 0.007. This series of CRMs can be used in the calibration of instruments and validation of analytical methods.
Key words: water activity; certified reference material; osmotic coefficient; sodium chloride; lithium chloride; uncertainty
引用本文：郑涵，王海峰，张艾蕊，等. 系列水分活度标准物质的研制[J]. 化学试剂，2024，46(3)：105-111 .
【合成与工艺技术】
一种三重对称硫杂扭曲多环芳烃的合成
邹肖，张宁琪，王宝军，张强*，张勇奇，汪艳，张田雷
（ 陕西理工大学 化学与环境科学学院 陕西省催化基础与应用重点实验室，陕西 汉中 732000）
摘要：硫杂多环芳烃具有并苯类物质的独特导电作用和光合作用中能够提高导电作用和光电效率的独特优势。围绕硫杂多环芳烃，以1,3,5-三(2-溴苯基)苯和苯并噻吩-2-硼酸通过钯催化的 Suzuki反应得到苯并噻吩结构的寡聚苯撑分子，苯并噻吩结构的寡聚苯撑分子在FeCl3作用下氧化脱氢环化合成了三重硫杂扭曲多环芳烃分子。中间体和产物的结构通过核磁共振波谱，质谱进行了表征。三硫杂多环芳烃的合成丰富了硫杂多环芳烃的种类，为合成更大共轭体系的三重硫杂扭曲多环芳烃提供了研究基础，三重硫杂扭曲多环芳烃分子为有机半导体材料，发光材料太阳能电池，光电二极管等分子器件提供的重要的候选材料。
关键词：硫杂多环芳烃；Suzuki反应；Scholl反应
中图分类号：O625 文献标识码：A 文章编号：0258-3283（2024）03-0112-06
DOI：10.13822/j.cnki.hxsj.2023.0702
Synthesis of a New Sulfur Heterocyclic Aromatic Hydrocarbons Zou Xiao, Zhang Ning-qi, Wang Bao-jun, Zhang Qiang*, Zhang Yong-qi, Wang Yan, Zhang Tian-lei (Shaanxi Key Laboratory of Catalysis, School of Chemistry and Environmental Science, Shaanxi University of Technology, Hanzhong 732000, China)
Abstract: Sulfur heterocyclic aromatic hydrocarbons have the unique conductivity of benzo compounds and the unique advantages of improving conductivity and photoelectric efficiency in photosynthesis. Oligophenylene with benzothiophene structure was synthesized by the palladium-catalyzed Suzuki reaction of 1,3,5-tri (2-bromophenyl) benzene and benzothiophene-2-boric acid around sulfur heteropolycyclic aromatic hydrocarbons. Trithiophene twisted polycyclic aromatic hydrocarbons were synthesized by the oxidative dehydrogenation of oligophenylene with FeCl3. The structures of the intermediates and products were characterized by NMR and MS. The synthesis of Trisulfide heteropolycyclic aromatic hydrocarbons enriches the family of Sulfur heteropolycyclic aromatic hydrocarbons and provides a research platform for the synthesis of triple sulfur hetero twisted polycyclic aromatic hydrocarbons with larger conjugated systems. Twisted triplethiapolycyclic aromatic hydrocarbon molecules could be employed as the important candidates for organic semiconductor materials, light-emitting materials, solar cells, and photodiodes as well as other molecular devices.
Key words: sulfur heterocyclic aromatic hydrocarbons; Suzuki reaction; Scholl reaction
引用本文：邹肖, 张宁琪, 王宝军, 等. 一种三重对称硫杂扭曲多环芳烃的合成[J]. 化学试剂, 2024, 46(3)：112-117.
