Progress in clean synthesis technology and application of rubber accelerator NS

doi:10.11949/0438-1157.20200659

Abstract

Abstract:

Ulfonamides rubber vulcanization accelerators can be divided into aldehydes, thiurams, thioureas, dithiocarbamates, thiazoles, guanidines, xanthates, and sulfenamides according to their chemical structure. Among them, sulfenamide accelerators have the advantages of long anti-scorch time, high vulcanization activity, high vulcanization flatness, and excellent mechanical properties, and are most widely used. Compared with the other sulfenamide accelerators, accelerator NS (N-tert-butyl-2-benzothiazolesulfenamide, TBBS) does not produce carcinogenic toxic nitrosamines in the process of vulcanization, so it is known as“standard accelerator”. The traditional method for synthesis of accelerator NS with sodium hypochlorite as oxidant is reviewed, and the green synthetic processes such as catalytic oxidation, chlorine oxidation, electrolytic oxidation and hydrogen peroxide oxidation are summarized. A brief overview of the application of the microreactor in the synthesis accelerator NS is provided. At the same time, the applications of accelerator NS in the fields of natural rubber, styrene-butadiene rubber, silica-filled rubber modifier and synthetic phosphoramidate were also introduced.

Key words: rubber accelerator NS, catalysis, oxidation, H₂O₂, microreactor

摘要：

橡胶硫化促进剂按照化学结构可以分为醛胺类、秋兰姆类、硫脲类、二硫代氨基甲酸盐类、噻唑类、胍类、黄原酸盐类和次磺酰胺类等，其中次磺酰胺类促进剂具有抗烧焦时间长、硫化活性大、硫化平坦性高、力学性能优良等优点，应用最为广泛。促进剂NS（N-叔丁基-2-苯并噻唑次磺酰胺，TBBS）与其他次磺酰胺类促进剂相比，因在硫化过程中不产生致癌毒性物质亚硝胺，被誉为“标准促进剂”。本文回顾了以次氯酸钠为氧化剂合成促进剂NS的传统方法；综述了催化氧化法、氯气氧化法、电解氧化法和双氧水氧化法等绿色合成工艺；简要概述了微通道反应器在合成促进剂NS方面的工业应用。同时简介了促进剂NS在天然橡胶、丁苯橡胶、二氧化硅填充橡胶的改性剂以及合成氨基磷酸酯等领域的应用。

关键词: 橡胶促进剂NS, 催化, 氧化, 双氧水, 微反应器

CLC Number:

TQ 330.38

ZHANG Tianyong, YANG Kunlong, CUI Xianbao, LI Bin, SONG Yuxin, JIANG Shuang. Progress in clean synthesis technology and application of rubber accelerator NS[J]. CIESC Journal, 2021, 72(2): 876-885.

张天永, 杨坤龙, 崔现宝, 李彬, 宋禹昕, 姜爽. 橡胶促进剂NS的绿色合成工艺与应用研究进展[J]. 化工学报, 2021, 72(2): 876-885.

Figures/Tables 2

References 73

1	王树华. 橡胶助剂行业自动化进程回顾及发展展望[J]. 中国橡胶, 2016, 32(3): 16-19.
	Wang S H. Review and development prospect of automation process in rubber additives industry[J]. China Rubber, 2016, 32(3): 16-19.
2	王仰东, 孙德江, 许春华. 科技创新推动橡胶助剂行业的“绿色”发展[J]. 中国橡胶, 2007, 23(10): 15-18.
	Wang Y D, Sun D J, Xu C H. Scientific and technological innovation promotes the “green” development of rubber additive industry[J]. China Rubber, 2007, 23(10): 15-18.
3	庞松, 徐新建, 陈家辉, 等. 硫化时间对NR/BR并用胶中交联密度的分布以及胶料耐磨性的影响[J]. 弹性体, 2019, 29(5): 11-16.
	Pang S, Xu X J, Chen J H, et al. Effect of curing time on distribution of crosslinking density in NR/BR blends and wear resistance of rubber compounds[J]. China Elastomerics, 2019, 29(5): 11-16.
4	郭飞, 张兆想, 宋炜, 等. 橡胶硫化过程数值模拟研究进展[J]. 化工学报, 2020, 71(8): 3393-3402.
	Guo F, Zhang Z X, Song W, et al. Research progress in numerical simulation of rubber vulcanization[J]. CIESC Journal, 2020, 71(8): 3393-3402.
5	梁馨元, 张磊, 刘琳琳, 等. 基于分子动力学的橡胶聚合物计算机辅助设计方法[J]. 化工学报, 2019, 70(2): 525-532.
	Liang X Y, Zhang L, Liu L L, et al. Study on rubber polymer using computer-aided molecular design method based on molecular dynamics[J]. CIESC Journal, 2019, 70(2): 525-532.
6	Zhang P, Zhao F, Yuan Y, et al. Network evolution based on general-purpose diene rubbers/sulfur/TBBS system during vulcanization (Ⅰ)[J]. Polymer, 2010, 51(1): 257-263.
7	Milani G, Milani F. NR sulphur vulcanization: interaction study between TBBS and DPG by means of a combined experimental rheometer and meta-model best fitting strategy[J]. Journal of Computational Methods in Sciences and Engineering, 2016, 16(2): 417-436.
8	Rong G Z, Chen Y S, Wang L, et al. A benzoxazole sulfenamide accelerator: synthesis, structure, property, and implication in rubber vulcanization mechanism[J]. Journal of Applied Polymer Science, 2014, 131(6): 39699.
9	Sun J T, Wang L L, Liu X L, et al. The preparation of multifunctional accelerators derived from tea phenols and their use in rubber compounds[J]. Journal of Elastomers and Plastics, 2018, 50(1): 58-70.
10	吴沫, 姚丽年. 次磺酰胺类橡胶硫化促进剂的生产与合成工艺现状[J]. 精细石油化工, 1990, (6): 44-47.
	Wu M, Yao L N. Production and synthesis process status of sulfenamide rubber vulcanization accelerators[J]. Fine Petrochemicals, 1990, (6): 44-47.
11	杨昌金, 廖禄生, 王兵兵, 等. 促进剂NS对环氧化天然橡胶硫化特性与力学性能的影响[J]. 合成材料老化与应用, 2018, 7(6): 39-41.
	Yang C J, Liao L S, Wang B B, et al. Effect of accelerator NS on cure and mechanical properties of epoxidized natural rubber[J]. Synthetic Materials Aging and Application, 2018, 7(6): 39-41.
12	Marzocca A J, Mansilla M A. Vulcanization kinetic of styrene-butadiene rubber by sulfur/TBBS[J]. Journal of Applied Polymer Science, 2006, 101(1): 35-41.
13	Marzocca A J, Mansilla M A. Analysis of network structure formed in styrene-butadiene rubber cured with sulfur/TBBS system[J]. Journal of Applied Polymer Science, 2007, 103(2): 1105-1112.
14	赵泽鹏, 雷娟, 陈晓博, 等. 苯并噻唑次磺酰胺类促进剂对钕系顺丁橡胶胶料性能的影响[J]. 橡胶工业, 2018, 65(9): 1026-1028.
	Zhao Z P, Lei J, Chen X B, et al. Effects of benzothiazole sulfenamide accelerators on properties of neodymium butadiene rubber compound[J]. China Rubber Industry, 2018, 65(9): 1026-1028.
15	周禾大. 促进剂NS合成工艺研究[J]. 精细化工原料及中间体, 2008, (6): 16-18.
	Zhou H D. Synthesis techniques of rubber accelerator NS[J]. Fine Chemical Industrial Raw Materials Intermediates, 2008, (6): 16-18.
16	万大明. 关于橡胶促进剂TBBS的合成及其市场前景[J]. 特种橡胶制品, 2000, 21(6): 54-57.
	Wan D M. Synthesis and prospect of rubber accelerator TBBS[J]. Special Purpose Rubber Products, 2000, 21(6): 54-57.
17	徐万平, 邓凤霞, 张征林, 等. 硫化促进剂NS的合成研究[J]. 精细化工, 2000, 17(5): 277-279.
	Xu W P, Deng F X, Zhang Z L, et al. Synthesis of vulcanization accelerator NS[J]. Fine Chemicals, 2000, 17(5): 277-279.
18	杜孟成, 赵红霞, 李云峰, 等. 氧气氧化法促进剂NS在全钢子午线轮胎胎面胶中的应用试验[J]. 橡胶科技, 2016, 14(2): 20-22.
	Du M C, Zhao H X, Li Y F, et al. Application of accelerator NS produced by oxygen oxidation process in the tread compound of TBR tire[J]. Rubber Science and Technology, 2016, 14(2): 20-22.
19	王东. 促进剂TBBS开发前景光明[J]. 精细化工原料及中间体, 2007, (5): 32-34.
	Wang D. The development prospect of accelerator TBBS is bright[J]. Fine Chemical Industrial Raw Materials and Intermediates, 2007, (5): 32-34.
20	孙风娟. 粗促进剂M钠盐合成促进剂TBBS新工艺的研究[J]. 橡胶科技, 2019, 17(5): 257-260.
	Sun F J. Study on accelerator TBBS synthetic process using crude accelerator M sodium salt[J]. Rubber Science and Technology, 2019, 17(5): 257-260.
21	刘万兴. 次磺酰胺类硫化促进剂NS的合成工艺研究[J]. 云南化工, 2019, 46(4): 54-55+59.
	Liu W X. Study on synthesis of sulfur accelerator NS[J]. Yunnan Chemical Technology, 2019, 46(4): 54-55+59.
22	马英杰, 宫志杰, 田苗. 促进剂N-叔丁基-2-苯并噻唑次磺酰胺的生产方法: 102285939A[P]. 2011-12-21.
	Ma Y J, Gong Z J, Tian M. Production method of accelerator N-tert-butyl-2-benzothiazole sulfenamide: 102285939A[P]. 2011-12-21.
23	李树东. 以次氯酸钠为氧化剂合成橡胶硫化促进剂NS的方法: 104557770A[P]. 2015-4-29.
	Li S D. Method of synthesizing rubber vulcanization accelerator NS with sodium hypochlorite as oxidant: 104557770A[P]. 2015-4-29.
24	朱军. 溶剂法生产橡胶硫化促进剂NS的方法: 103524453A[P]. 2014-01-22.
	Zhu J. Solvent method for producing rubber vulcanization accelerator NS: 103524453A [P]. 2014-01-22.
25	朱嘉震, 赵新远, 田旭, 等. 氧气氧化法制备橡胶硫化促进剂TBBS: 108586384A[P]. 2018-09-28.
	Zhu J Z, Zhao X Y, Tian X, et al. Preparation of rubber vulcanization accelerator TBBS by oxygen oxidation: 108586384A[P]. 2018-09-28.
26	Mukminova G R, Avrutskaya I A, Novikov V T. Electrochemical synthesis of tert-butyl-2-benzothiazolesulfenamide[J]. Russian Journal of Electrochemistry, 1999, 35(8): 841-845.
27	袁冰芯, 李恒, 唐珊瑜. 一种电化学合成具有S—N键的次磺酰胺化合物的方法: 109338403A[P]. 2019-02-15.
	Yuan B X, Li H, Tang S Y. A method for electrochemical synthesis of sulfenamide compounds with S—N bond: 109338403A[P]. 2019-02-15.
28	彭华龙, 王小萍, 罗远芳, 等. 促进剂NS的制备及其硫化特性研究[J]. 橡胶工业, 2008, 7: 412-415.
	Peng H L, Wang X P, Luo Y F, et al. Study on preparation and vulcanization characteristics of accelerator NS[J]. China Rubber Industry, 2008, 7: 412-415.
29	张卫昌, 庄苏桔, 殷守华, 等. 促进剂NS的合成及其在胎面胶中的应用[J]. 特种橡胶制品, 2007, 28(6): 17-19.
	Zhang W C, Zhuang S J, Yin S H, et al. Synthesis of rubber accelerator NS and its application to tread compound[J]. Special Purpose Rubber Products, 2007, 28(6): 17-19.
30	朱军. 生产橡胶促进剂NS的方法: 10358976A[P]. 2014-01-15.
	Zhu J. Method for producing rubber accelerator NS: 10358976A[P]. 2014-01-15.
31	王秀猛. 一种环保型N-叔丁基-2-苯并噻唑次磺酰胺(NS)合成工艺: 108727302A[P]. 2018-11-02.
	Wang X M. An environmentally friendly N-tert-butyl-2-benzothiazole sulfenamide(NS) synthesis process: 108727302A[P]. 2018-11-02.
32	Tang S Y, Liu Y, Li L J, et al. Scalable electrochemical oxidant-and metal-free dehydrogenative coupling of S-H/N-H[J]. Organic & Biomolecular Chemistry, 2019, 17(6): 1370-1374.
33	Choi S S, Nah C, Jo B W. Properties of natural rubber composites reinforced with silica or carbon black: influence of cure accelerator content and filler dispersion[J]. Polymer International, 2003, 52(8): 1382-1389.
34	Carr E L, Smith G E P, Alliger G. Thiazolesulfenamides1[J]. The Journal of Organic Chemistry, 1949, 14(6): 921-934.
35	Taniguchi N. Copper-catalyzed formation of sulfur-nitrogen bonds by dehydrocoupling of thiols with amines[J]. European Journal of Organic Chemistry, 2010, 2010(14): 2670-2673.
36	徐万平, 邓凤霞. 硫化促进剂N-叔丁基-2-苯并噻唑(TBBS)的合成工艺综述[J]. 化工时刊, 2000, (3): 42-44.
	Xu W P, Deng F X. Process summarization of TBBS vulcanization accelerator[J]. Chemical Industry Times, 2000, (3): 42-44.
37	林闯. 浅析硫化促进剂TBBS的合成[J]. 中国化工贸易, 2013, (7): 402.
	Lin C. Analysis on the synthesis of vulcanization accelerator TBBS[J]. China Chemical Trade, 2013, (7): 402.
38	Robert H. Manufacture of branched chain sulfonamides: US2807620[P]. 1957.
39	张越, 李小云, 李建军. 橡胶硫化促进剂NS的合成[J]. 河北师范大学学报, 1998, 22(2): 82-84+94.
	Zhang Y, Li X Y, Li J J. Using crude 2-mercaptobenzothiazole(M) to prepared N-tert-butylbenzothiazole-2-sulfenamide(NS) directly[J]. Journal of Hebei Normal University, 1998, 22(2): 82-84+94.
40	Zhan N X, Zhang Y, Wang X Z. Solubility of N-tert-butylbenzothiazole-2-sulfenamide in several pure and binary solvents[J]. Journal of Chemical and Engineering Data, 2019, 64(3): 1051-1062.
41	蔡玉照. 硫化促进剂NS的新型合成工艺研究[J]. 山东化工, 2013, 42(8): 5-6.
	Cai Y Z. Study on a new synthetic process of vulcanization accelerator NS[J]. Shandong Chemical Industry, 2013, 42(8): 5-6.
42	周禾大. 硫化促进剂NS合成工艺研究[J]. 江苏化工, 2008, 36(2): 27-29.
	Zhou H D. Synthesis techniques of accelerator NS[J]. Jiangsu Chemical Industry, 2008, 36(2): 27-29.
43	曹耀强, 肖波, 卜晓光. 硫化促进剂TBBS合成研究[J]. 石化技术与应用, 2004, 22(4): 252-256.
	Cao Y Q, Xiao B, Bu X G. Synthesis of vulcanization accelerator TBBS[J]. Petrochemical Technology & Application, 2004, 22(4): 252-256.
44	朱嘉震, 王金才, 田旭, 等. 利用微通道反应器制备橡胶促进剂NS的方法: 106866578A[P]. 2017-06-20.
	Zhu J Z, Wang J C, Tian X, et al. Preparation of rubber accelerator NS in microchannel reactor: 106866578A[P]. 2017-06-20.
45	王文博, 杜孟成, 郑崇纳, 等. 橡胶硫化促进剂NS废水处理工艺: 101407344[P]. 2009-04-15.
	Wang W B, Du M C, Zheng C N, et al. Process for treating waste water of rubber vulcanization accelerator NS production: 101407344[P]. 2009-04-15.
46	Rattanangkool E, Krailat W, Vilaivan T, et al. Hypervalent iodine(Ⅲ)-promoted metal-free S-H activation: an approach for the construction of S-S, S-N, and S-C bonds[J]. European Journal of Organic Chemistry, 2014, 2014(22): 4795-4804.
47	Lee C, Lim Y N, Jang H Y. Copper-catalyzed synthesis of N-formyl/acylsulfenamides and -thiosulfonamides[J]. European Journal of Organic Chemistry, 2015, 2015(27): 5934-5938.
48	Sakagami K, Jin X J, Suzuki K, et al. Synthesis of N-acylsulfenamides through aerobic cross dehydrogenative coupling of thiols and amides by supported copper hydroxide catalyst[J]. Chemistry Letters, 2016, 45(2): 173-175.
49	Raymond J. Process for the preparation of thiazolesulphenamides: US4182873[P]. 1980.
50	Kleinwallstadt H Z, Obernburgeisenbach L E, Erlenbach M B. Process for the production of thiazoly-2-sulphcnamidcs: US4670556A[P]. 1987-06-02.
51	杜孟成, 刘红, 陈宝喜, 等. 氧气氧化法合成促进剂NS的工艺及其应用[J]. 轮胎工业, 2011, 31(8): 484-488.
	Du M C, Liu H, Chen B X, et al. Synthesis of accelerator NS by oxygen oxidation process and its applications[J]. Tire Industry, 2011, 31(8): 484-488.
52	尹红伟. 促进剂N-叔丁基苯并噻唑次磺酰胺生产中的催化剂及制备方法: 102309986A[P]. 2012-01-11.
	Yin H W. Catalyst and preparation method for the production of accelerant N-tert-butylbenzothiazole sulfenamide: 102309986A[P]. 2012-01-11.
53	Dou Y C, Huang X, Wang H, et al. Reusable cobalt-phthalocyanine in water: efficient catalytic aerobic oxidative coupling of thiols to construct S-N/S-S bonds[J]. Green Chemistry, 2017, 19(11): 2491-2495.
54	Yang L T, Li S D, Dou Y C, et al. TEMPO-catalyzed aerobic oxidative coupling of thiols for metal-free formation of S-N/S-S bonds[J]. Asian Journal of Organic Chemistry, 2017, 6(3): 265-268.
55	刘小培, 邢青峰, 董学亮, 等. N-叔丁基-2-苯并噻唑次磺酰胺的合成工艺研究进展[J]. 化学研究, 2012, 23(3): 103-105.
	Liu X P, Xing Q F, Dong X L, et al. Progress of synthesis technology of N-tert-butyl-2-benzothiazole sulfenamide[J]. Chemical Research, 2012, 23(3): 103-105.
56	Torii S, Tanaka H, Ukida M. Electrosynthesis of hetero-hetero atom bonds. 2. An efficient preparation of (2-bcnzothiazoiyl)-and thiocarbamoylsulfenamides by electrolytic cross-coupling reaction of 2-mercaptobenzothiazole, bis(2-benzothiazolyl) disulfide, and/or bis(dialkylthiocarbamoyl)disulfides with various amines[J]. The Journal of Organic Chemistry, 1978, 13(16): 3223-3227.
57	丁俊杰, 王飞. 电解氧化法制备促进剂NS的工艺研究[J]. 中国橡胶, 2018, 34(1): 48-50.
	Ding J J, Wang F. Study on the preparation of accelerator NS by electrolytic oxidation[J]. China Rubber, 2018, 34(1): 48-50.
58	李中贤, 刘小培, 王俊伟, 等. 一种水相中电解法合成橡胶硫化促进剂TBBS工艺: 104109879A[P]. 2014-10-22.
	Li Z X, Liu X P, Wang J W, et al. A process for synthesizing rubber vulcanization accelerator TBBS by electrolysis in aqueous phase: 104109879A[P]. 2014-10-22.
59	Mukminova G R, Simonov M D, Chernykh G V, et al. Electrosynthesis of N-tert-butyl-2-benzothiazolesulfenamide[J]. Russian Journal of Electrochemistry, 2001, 37(1): 107-111.
60	刘洋, 曾庆乐, 唐红艳, 等. 绿色化学试剂过氧化氢在有机合成中的应用研究进展[J]. 有机化学, 2011, 31(7): 986-996.
	Liu Y, Zeng Q L, Tang H Y, et al. Progress on organic synthesis using hydrogen peroxide as a green chemical reagent[J]. Chinese Journal of Organic Chemistry, 2011, 31(7): 986-996.
61	Dormauen S G, Temse L F, Hoevenen D S, et al. Process for preparing storage-stable benzothiazolyl sulfenamides: US0167340A1[P]. 2004-08-26.
62	谭雄文, 徐军才. 橡胶硫化促进剂NS的合成研究[J]. 广东化工, 2006, 33(5): 16-17.
	Tan X W, Xu J C. Synthesis of rubber accelerator NS[J]. Guangdong Chemical Industry, 2006, 33(5): 16-17.
63	贾太轩, 宋国全, 郭尧, 等. N-叔丁基-2-苯并噻唑次磺酰胺制备及其光谱分析[J]. 光谱学与光谱分析, 2016, 36(7): 2213-2216.
	Jia T X, Song G Q, Guo Y, et al. Study on the preparation of N-tert-butyl-2-benzothiazole sulfenamide and its spectral analysis[J]. Spectroscopy and Spectral Analysis, 2016, 36(7): 2213-2216.
64	朱军. 以双氧水为氧化剂两步法合成橡胶硫化促进剂NS的方法: 102838562A[P]. 2012-12-26.
	Zhu J. Two-step synthesis of rubber vulcanization accelerator NS with hydrogen peroxide as oxidant: 102838562A[P]. 2012-12-26.
65	Kobayashi J, Mori Y, Kobayashi S. Multiphase organic synthesis in microchannel reactors[J]. Chemistry-an Asian Journal, 2006, 1(1/2): 22-35.
66	Ulissi Z W, Strano M S, Braatz R D. Control of nano and microchemical systems[J]. Computers & Chemical Engineering, 2013, 51: 149-156.
67	Makarshin L L, Pai Z P, Parmon V N. Microchannel systems for fine organic synthesis[J]. Russian Chemical Reviews, 2016, 85(2): 139-155.
68	Ghorai S, Jalan A K, Roy M, et al. Tuning of accelerator and curing system in devulcanized green natural rubber compounds[J]. Polymer Testing, 2018, 69: 133-145.
69	Gradwell M H S, van der Merwe M J. 2-t-Butylbenzothiazole sulfenamide accelerated sulfur vulcanization of polyisoprene[J]. Rubber Chemistry and Technology, 1999, 72(1): 65-73.
70	程涛. 丁苯橡胶的合成工艺及发展[J]. 化工设计通讯, 2017, 43(1): 60.
	Cheng T. Synthesis and development of styrene butadiene rubber[J]. Chemical Engineering Design Communication, 2017, 43(1): 60.
71	Sedlova N G, Shilov I B, Fomin S V, et al. Synthesis of a modifier for rubbers with silica-filler by reaction of N-tert-butyl-2-benzothiazolylsulfenamide with trimethylolpropane triglycidyl ether and characterization of the reaction product[J]. Russian Journal of Applied Chemistry, 2018, 91(7): 1188-1192.
72	Oliveira F M, Barbosa L C A, Ismail F M D. The diverse pharmacology and medicinal chemistry of phosphoramidates-a review[J]. RSC Advances, 2014, 4(36): 18998-19012.
73	Brownbridge P, Jowett I C. On the reaction of benzothiazol-2-yl sulfenamides with phosphites[J]. Phosphorus Sulfur and Silicon and the Related Elements, 1988, 35(3/4): 311-318.

[1]	Xuejin YANG, Jintao YANG, Ping NING, Fang WANG, Xiaoshuang SONG, Lijuan JIA, Jiayu FENG. Research progress in dry purification technology of highly toxic gas PH₃ [J]. CIESC Journal, 2023, 74(9): 3742-3755.
[2]	Baiyu YANG, Yue KOU, Juntao JIANG, Yali ZHAN, Qinghong WANG, Chunmao CHEN. Chemical conversion of dissolved organic matter in petrochemical spent caustic along a wet air oxidation pretreatment process [J]. CIESC Journal, 2023, 74(9): 3912-3920.
[3]	Yepin CHENG, Daqing HU, Yisha XU, Huayan LIU, Hanfeng LU, Guokai CUI. Application of ionic liquid-based deep eutectic solvents for CO₂ conversion [J]. CIESC Journal, 2023, 74(9): 3640-3653.
[4]	Jintong LI, Shun QIU, Wenshou SUN. Oxalic acid and UV enhanced arsenic leaching from coal in flue gas desulfurization by coal slurry [J]. CIESC Journal, 2023, 74(8): 3522-3532.
[5]	Kaixuan LI, Wei TAN, Manyu ZHANG, Zhihao XU, Xuyu WANG, Hongbing JI. Design of cobalt-nitrogen-carbon/activated carbon rich in zero valent cobalt active site and application of catalytic oxidation of formaldehyde [J]. CIESC Journal, 2023, 74(8): 3342-3352.
[6]	Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3242-3255.
[7]	Yaxin CHEN, Hang YUAN, Guanzhang LIU, Lei MAO, Chun YANG, Ruifang ZHANG, Guangya ZHANG. Advances in enzyme self-immobilization mediated by protein nanocages [J]. CIESC Journal, 2023, 74(7): 2773-2782.
[8]	Xiaoling TANG, Jiarui WANG, Xuanye ZHU, Renchao ZHENG. Biosynthesis of chiral epichlorohydrin by halohydrin dehalogenase based on Pickering emulsion system [J]. CIESC Journal, 2023, 74(7): 2926-2934.
[9]	Bin LI, Zhenghu XU, Shuang JIANG, Tianyong ZHANG. Clean and efficient synthesis of accelerator CBS by hydrogen peroxide catalytic oxidation method [J]. CIESC Journal, 2023, 74(7): 2919-2925.
[10]	Yuming TU, Gaoyan SHAO, Jianjie CHEN, Feng LIU, Shichao TIAN, Zhiyong ZHOU, Zhongqi REN. Advances in the design, synthesis and application of calcium-based catalysts [J]. CIESC Journal, 2023, 74(7): 2717-2734.
[11]	Pan LI, Junyang MA, Zhihao CHEN, Li WANG, Yun GUO. Effect of the morphology of Ru/α-MnO₂ on NH₃-SCO performance [J]. CIESC Journal, 2023, 74(7): 2908-2918.
[12]	Tan ZHANG, Guang LIU, Jinping LI, Yuhan SUN. Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts [J]. CIESC Journal, 2023, 74(6): 2264-2280.
[13]	Chen WANG, Xiufeng SHI, Xianfeng WU, Fangjia WEI, Haohong ZHANG, Yin CHE, Xu WU. Preparation of Mn₃O₄ catalyst by redox method and study on its catalytic oxidation performance and mechanism of toluene [J]. CIESC Journal, 2023, 74(6): 2447-2457.
[14]	Lei MAO, Guanzhang LIU, Hang YUAN, Guangya ZHANG. Efficient preparation of carbon anhydrase nanoparticles capable of capturing CO₂ and their characteristics [J]. CIESC Journal, 2023, 74(6): 2589-2598.
[15]	Xueyan WEI, Yong QIAN. Experimental study on the low to medium temperature oxidation characteristics and kinetics of micro-size iron powder [J]. CIESC Journal, 2023, 74(6): 2624-2638.