Recent progress on titanosilicate zeolite catalyzed green oxidation technologies

doi:10.16085/j.issn.1000-6613.2025-0002

Abstract

Abstract:

Due to environmental friendliness and high atomic economy, titanosilicate zeolite catalyzed selective oxidation have raised greenization revolution in the field of oxidation, which has attracted much attention in recent years. This article firstly reviewed the recent progress of titanosilicate zeolite, mainly focusing on the structure, preparation method and catalytic oxidation applications of TS-1, Ti MWW, Ti MOR and Ti/HMS zeolites that have been widely used in industry. Subsequently, the developed green oxidation technologies including propylene epoxidation to propylene oxide, ketone ammoximation to ketoxime and phenol hydroxylation to dihydroxybenzene, and their industrial applications and recent research progresses, were well summarized. Finally, based on the current status of green catalytic oxidation technologies with titanosilicate zeolite, it’s pointed out that reducing the production cost of titanosilicate zeolite, accelerating the development of new catalytic green oxidation technologies and developing catalytic oxidation technologies using in-situ generated hydrogen peroxide were of great significance and should be the key directions for future research and development.

Key words: titanosilicate zeolite, hydrogen peroxide, olefin epoxidation, ketone ammoximation, phenol hydroxylation, industrial application

摘要：

由于环境友好、原子利用率高等特点，基于钛硅分子筛催化的选择氧化技术掀起氧化领域的绿色化革命，受到了人们的极大关注。鉴于此，本文首先综述了钛硅分子筛材料的研究进展，重点介绍了已实现工业应用的钛硅分子筛TS-1、Ti-MWW、Ti-MOR及Ti/HMS的结构、制备方法及催化氧化应用；随后总结了基于这些钛硅分子筛催化材料开发出的丙烯环氧化制环氧丙烷、酮氨肟化制酮肟、苯酚羟基化制苯二酚等绿色氧化技术及其工业应用情况，并介绍了这些绿色氧化过程的最新研究动态；最后结合基于钛硅分子筛的绿色催化氧化技术的现状，指出降低钛硅分子筛生产成本、加快催化绿色氧化新技术开发及发展原位产生和利用过氧化氢的催化氧化技术等均有重要意义，是未来研究和开发的重点方向。

关键词: 钛硅分子筛, 过氧化氢, 烯烃环氧化, 酮氨肟化, 苯酚羟基化, 工业应用

CLC Number:

TQ05

JIN Shaoqing, FAN Xueyan, TANG Zhimou, WANG Yanli, WANG Darui, SUN Hongmin, YANG Weimin. Recent progress on titanosilicate zeolite catalyzed green oxidation technologies[J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2907-2918.

金少青, 范雪研, 唐智谋, 王衍力, 王达锐, 孙洪敏, 杨为民. 基于钛硅分子筛催化的绿色氧化技术进展[J]. 化工进展, 2025, 44(5): 2907-2918.

Figures/Tables 8

References 90

91	丁姜宏. 羰基化合物以及衍生物的绿色催化合成[D]. 上海: 华东师范大学, 2016.
	DING Jianghong. Green catalytic synthesis of carbonyl compounds and derivatives[D]. Shanghai: East China Normal University, 2016.
92	杨玉林. MOR和MFI拓扑结构钛硅分子筛的液相氧化性能研究[D]. 上海: 华东师范大学, 2016.
	YANG Yulin. Study on liquid phase oxidation performance of MOR and MFI topological titanium silicalite molecular sieves[D]. Shanghai: East China Normal University, 2016.
93	尹金鹏, 梁晓航, 孙丹宇, 等. 钛硅分子筛合成及其催化环己酮氨肟化反应研究进展[J]. 化学推进剂与高分子材料, 2023, 21(4): 1-11.
	YIN Jinpeng, LIANG Xiaohang, SUN Danyu, et al. Research progress in synthesis of titanium silicalite and its catalytic cyclohexanone ammoximation reaction[J]. Chemical Propellants & Polymeric Materials, 2023, 21(4): 1-11.
94	林衍华, 陈秀宏, 王华文, 等. 苯二酚生产工艺进展[J]. 精细石油化工进展, 2002, 3(7): 28-31.
	LIN Yanhua, CHEN Xiuhong, WANG Huawen, et al. Progress in process of dihydroxybenzene[J]. Advances in Fine Fetrochemicals, 2002, 3(7): 28-31.
95	杜亚平. 苯二酚的开发与生产进展[J]. 上海化工, 2008, 33(3): 19-24.
	DU Yaping. Development and manufacture progress of dihydroxybenzene[J]. Shanghai Chemical Industry, 2008, 33(3): 19-24.
96	BELLUSSI Giuseppe, MILLINI Roberto, POLLESEL Paolo, et al. Zeolite science and technology at eni[J]. New Journal of Chemistry, 2016, 40(5): 4061-4077.
97	左轶, 刘民, 郭新闻. 钛硅分子筛的合成及其催化氧化反应研究进展[J]. 石油学报(石油加工), 2015, 31(2): 343-359.
1	薛金召, 牛小娟, 汪希领, 等. 国内环氧丙烷市场分析及技术进展[J]. 化工进展, 2015, 34(9): 3500-3506.
	XUE Jinzhao, NIU Xiaojuan, WANG Xiling, et al. Market analysis and technology progress of domestic propylene oxide[J]. Chemical Industry and Engineering Progress, 2015, 34(9): 3500-3506.
2	KUMAR Rawesh, SHAH Sneha, PARAMITA DAS Prangya, et al. An overview of caprolactam synthesis[J]. Catalysis Reviews, 2019, 61(4): 516-594.
3	RUAN Hao, WANG Kaiwei, BING Changhao, et al. Investigation of the Ti active site in TS-1 for phenol hydroxylation via seed and dissolution-recrystallization methods[J]. Molecular Catalysis, 2024, 568: 114524.
4	史延强, 夏玥穜, 温朗友, 等. 过氧化氢及其基本有机化学品绿色合成技术[J]. 化工进展, 2021, 40(4): 2048-2059.
	SHI Yanqiang, XIA Yuetong, WEN Langyou, et al. Hydrogen peroxide and its green synthesis of basic organic chemicals[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2048-2059.
5	TARAMASSO Marco, PEREGO Giovanni, NOTARI Bruno. Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides: US4410501[P]. 1983-10-18.
6	谢伟, 刘月明, 汪玲玲, 等. 具有MWW结构钛硅分子筛的研究进展[J]. 催化学报, 2010, 31(5): 502-513.
	XIE Wei, LIU Yueming, WANG Lingling, et al. Recent advances in MWW-type titanosilicates[J]. Chinese Journal of Catalysis, 2010, 31(5): 502-513.
7	Jan PŘECH. Catalytic performance of advanced titanosilicate selective oxidation catalysts—A review[J]. Catalysis Reviews, 2018, 60(1): 71-131.
8	MILLINI Roberto, BELLUSSI Giuseppe, POLLESEL Paolo, et al. Beyond TS-1: Background and recent advances in the synthesis of Ti-containing zeolites[J]. Microporous and Mesoporous Materials, 2022, 346: 112286.
9	WU Peng, XU Hao. Micro-mesoporous metallosilicates: Synthesis, characterization, and catalytic applications[M]. Weinheim, Germany: Wiley-VCH, 2024.
10	WANG Jiawen, DUAN Ning, LI Pan, et al. Recent advances in the synthesis and application of TS-1 zeolite for green catalytic oxidation[J]. Advanced Sustainable Systems, 2025, 9(2): 2400719.
11	WANG Xiangsheng, GUO Xinwen, LI Gang. Synthesis of titanium silicalite (TS-1) from the TPABr system and its catalytic properties for epoxidation of propylene[J]. Catalysis Today, 2002, 74(1/2): 65-75.
12	KRAUSHAAR B, VAN HOOFF J H C. A new method for the preparation of titanium-silicalite (TS-1)[J]. Catalysis Letters, 1988, 1(4): 81-84.
13	李明丰, 郭新闻, 于桂燕, 等. 以de-[B]ZSM-5为母体的钛硅沸石Ti-SiZSM-5合成[J]. 石油化工, 1998, 27(5): 319-323.
	LI Mingfeng, GUO Xinwen, YU Guiyan, et al. The synthesis of Ti-SiZSM-5 using de-[B]ZSM-5 as precursor[J]. Petrochemical Technology, 1998, 27(5): 319-323.
14	许章林, 张盈珍, 郑禄彬. 杂原子沸石的二次合成及其表征——Ⅱ.含Ti、Fe杂原子沸石[J]. 分子催化, 1992, 6(5): 365-370.
	XU Zhanglin, ZHANG Yingzhen, ZHENG Lubin. The secondary synthesis of zeolites via framework substitution for aluminum Ⅱ. preparation and characterization of zeolite containing Ti and Fe elements[J]. Journal of Molecular Catalysis, 1992, 6(5): 365-370.
15	DENG Xiujuan, WANG Yuning, SHEN Lu, et al. Low-cost synthesis of titanium silicalite-1 (TS-1) with highly catalytic oxidation performance through a controlled hydrolysis process[J]. Industrial & Engineering Chemistry Research, 2013, 52(3): 1190-1196.
16	YANG Guoju, HAN Ji, LIU Yue, et al. The synthetic strategies of hierarchical TS-1 zeolites for the oxidative desulfurization reactions[J]. Chinese Journal of Chemical Engineering, 2020, 28(9): 2227-2234.
17	BAI Risheng, SONG Yue, BAI Ruobing, et al. Creation of hierarchical titanosilicate TS-1 zeolites[J]. Advanced Materials Interfaces, 2021, 8(4): 2001095.
18	SERRANO D P, SANZ R, PIZARRO P, et al. Tailoring the properties of hierarchical TS-1 zeolite synthesized from silanized protozeolitic units[J]. Applied Catalysis A: General, 2012, 435: 32-42.
19	YAO Yulin, YANG Zonghan, ZHENG Pengfei, et al. Enhancing the accessible TiO₆ concentration and the hydrophobicity of hierarchical TS-1 zeolites for alkene epoxidation and oxidative desulfurization[J]. Chemical Engineering Journal, 2023, 475: 146053.
20	LIU Meng, WANG Yaqing, CHEN Wenxia, et al. Synthesis of hierarchical titanium silicalite-1 by seed silanization for selective oxidation reactions[J]. Microporous and Mesoporous Materials, 2023, 350: 112458.
21	YUE MING bo, SUN MENG nan, XIE Fei, et al. Dry-gel synthesis of hierarchical TS-1 zeolite by using P123 and polyurethane foam as template[J]. Microporous and Mesoporous Materials, 2014, 183: 177-184.
22	DU Qi, GUO Yiping, WU Pei, et al. Facile synthesis of hierarchical TS-1 zeolite without using mesopore templates and its application in deep oxidative desulfurization[J]. Microporous and Mesoporous Materials, 2019, 275: 61-68.
23	SMEETS Valentin, GAIGNEAUX Eric M, DEBECKER Damien P. Hierarchical micro-/ macroporous TS-1 zeolite epoxidation catalyst prepared by steam assisted crystallization[J]. Microporous and Mesoporous Materials, 2020, 293: 109801.
24	WANG Yongrui, LIN Min, TUEL Alain. Hollow TS-1 crystals formed via a dissolution-recrystallization process[J]. Microporous and Mesoporous Materials, 2007, 102(1/2/3): 80-85.
25	XU Wenjing, LI Li, ZHANG Tianjun, et al. Tailoring porosity and titanium species of TS-1 zeolites via organic base-assisted sequential post-treatment[J]. Chemical Research in Chinese Universities, 2022, 38(1): 50-57.
26	刘巍, 郭冬冬, 邓东浩, 等. FAU型多级孔分子筛孔道结构的表征[J]. 石油化工, 2021, 50(1): 1-5.
	LIU Wei, GUO Dongdong, DENG Donghao, et al. Characterization of the channel structure of FAU-type hierarchical porous molecular sieves[J]. Petrochemical Technology, 2021, 50(1): 1-5.
27	WISSER Dorothea, HARTMANN Martin. 129Xe NMR on porous materials: Basic principles and recent applications[J]. Advanced Materials Interfaces, 2021, 8(4): 2001266.
28	WANG Baorong, PENG Xinxin, ZHANG Wenfeng, et al. Hierarchical TS-1 synthesized via the dissolution-recrystallization process: Influence of ammonium salts[J]. Catalysis Communications, 2017, 101: 26-30.
29	肖昱, 刘湛, 余申, 等. 具有高活性六配位Ti物种的多级孔TS-1分子筛的合成及应用[J]. 石油学报(石油加工), 2024, 40(5): 1157-1167.
	XIAO Yu, LIU Zhan, YU Shen, et al. Synthesis and application of hierarchical porous TS-1 zeolite with highly active six-coordinated Ti species[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2024, 40(5): 1157-1167.
30	LI Shiqing, Jie TUO, PENG Rusi, et al. Controllable construction of highly active Ti species in TS-1 zeotype by organic base treatment[J]. Catalysis Science & Technology, 2025, 15(3): 722-733.
31	WANG Baohe, GUO Yanke, ZHU Jing, et al. A review on titanosilicate-1 (TS-1) catalysts: Research progress of regulating titanium species[J]. Coordination Chemistry Reviews, 2023, 476: 214931.
32	WANG Yihao, WANG Kaiwei, WANG Fumin, et al. A review on the active sites for titanium species in zeolites: Coordination structure, synthetic strategies and activity[J]. Materials Chemistry Frontiers, 2025, 9(1): 8-29.
33	FAN Weibin, DUAN Renguan, YOKOI Toshiyuki, et al. Synthesis, crystallization mechanism, and catalytic properties of titanium-rich TS-1 free of extraframework titanium species[J]. Journal of the American Chemical Society, 2008, 130(31): 10150-10164.
34	GUO Qiang, SUN Dr Keju, FENG Prof Dr Zhaochi, et al. A thorough investigation of the active titanium species in TS-1 zeolite by in situ UV resonance Raman spectroscopy[J]. Chemistry: A European Journal, 2012, 18(43): 13854-13860.
35	WANG Yanli, YANG Hong, ZUO Yi, et al. New penta- and hexa-coordinated titanium sites in titanium silicalite-1 catalyst for propylene epoxidation[J]. Applied Catalysis B: Environmental, 2023, 325: 122396.
36	XU Wenjing, ZHANG Tianjun, BAI Risheng, et al. A one-step rapid synthesis of TS-1 zeolites with highly catalytically active mononuclear TiO6 species[J]. Journal of Materials Chemistry A, 2020, 8(19): 9677-9683.
37	WANG Yuyao, LI Li, BAI Risheng, et al. Amino acid-assisted synthesis of TS-1 zeolites containing highly catalytically active TiO₆ species[J]. Chinese Journal of Catalysis, 2021, 42(12): 2189-2196.
38	WANG Lingling, LIU Yueming, XIE Wei, et al. Highly efficient and selective production of epichlorohydrin through epoxidation of allyl chloride with hydrogen peroxide over Ti-MWW catalysts[J]. Journal of Catalysis, 2007, 246(1): 205-214.
39	宋芬. 新一代钛硅分子筛催化剂Ti-MWW在环境友好化学过程中的应用[D]. 上海: 华东师范大学, 2007.
	SONG Fen. Application of Ti-MWW, a new generation of Ti-Si molecular sieve catalyst, in environmentally friendly chemical processes[D]. Shanghai: East China Normal University, 2007.
40	WU Peng, TATSUMI Takashi, KOMATSU Takayuki, et al. A novel titanosilicate with MWW structure. Ⅰ. Hydrothermal synthesis, elimination of extraframework titanium, and characterizations[J]. The Journal of Physical Chemistry B, 2001, 105(15): 2897-2905.
41	WU Peng, MIYAJI Takayuki, LIU Yueming, et al. Synthesis of Ti-MWW by a dry-gel conversion method[J]. Catalysis Today, 2005, 99(1/2): 233-240.
42	LIU Na, LIU Yueming, XIE Wei, et al. Hydrothermal synthesis of boron-free Ti-MWW with dual structure-directing agents[J]. Studies in Surface Science and Catalysis, 2007, 170: 464-469.
43	TANG Zhimou, YU Yunkai, LIU Wei, et al. Deboronation-assisted construction of defective Ti(OSi)₃OH species in MWW-type titanosilicate and their enhanced catalytic performance[J]. Catalysis Science & Technology, 2020, 10(9): 2905-2915.
44	JIN Shaoqing, WANG Zhendong, TAO Guiju, et al. UV resonance Raman spectroscopic insight into titanium species and structure-performance relationship in boron-free Ti-MWW zeolite[J]. Journal of Catalysis, 2017, 353: 305-314.
45	ZHANG Shilin, JIN Shaoqing, TAO Guiju, et al. The evolution of titanium species in boron-containing Ti-MWW zeolite during post-treatment revealed by UV resonance Raman spectroscopy[J]. Microporous and Mesoporous Materials, 2017, 253: 183-190.
46	ZHANG Jie, JIN Shaoqing, DENG Donghao, et al. Insight into the formation of framework titanium species during acid treatment of MWW-type titanosilicate and the effect of framework titanium state on olefin epoxidation[J]. Microporous and Mesoporous Materials, 2021, 314: 110862.
47	罗强强, 金少青, 孙洪敏, 等. 液相酸溶液后补钛合成Ti-MWW分子筛[J]. 高等学校化学学报, 2021, 42(9): 2742-2751.
	LUO Qiangqiang, JIN Shaoqing, SUN Hongmin, et al. Post-synthesis of Ti-MWW zeolite via titanium incorporation in liquid acid solution[J]. Chemical Journal of Chinese Universities, 2021, 42(9): 2742-2751.
48	HUO Yuanling, ZHANG Yang, XU Wen, et al. Acid-modulated synthesis of Ti-MWW zeolites with rich framework Ti species for efficient epoxidation[J]. Industrial & Engineering Chemistry Research, 2020, 59(45): 19929-19937.
49	XU Bowen, DENG Mengshan, LIN Kehang, et al. Acid-modulated synthesis of ultra-thin Ti-MWW zeolite nanosheets for the efficient epoxidation of cycloalkenes with tert-butyl hydroperoxide[J]. Journal of Catalysis, 2024, 429: 115256.
50	FAN Xueyan, HU Wende, JIN Shaoqing, et al. Effect of P modification on the structure and catalytic performance of Ti-MWW zeolite[J]. Microporous and Mesoporous Materials, 2022, 336: 111887.
51	XU Le, HUANG Dading, LI Chengeng, et al. Construction of unique six-coordinated titanium species with an organic amine ligand in titanosilicate and their unprecedented high efficiency for alkene epoxidation[J]. Chemical Communications, 2015, 51(43): 9010-9013.
52	YIN Jinpeng, XU Hao, WANG Bowen, et al. Highly selective 1-pentene epoxidation over Ti-MWW with modified microenvironment of Ti active sites[J]. Catalysis Science & Technology, 2020, 10(17): 6050-6064.
53	WU Peng, NUNTASRI Duangamol, RUAN Juanfang, et al. Delamination of Ti-MWW and high efficiency in epoxidation of alkenes with various molecular sizes[J]. The Journal of Physical Chemistry B, 2004, 108(50): 19126-19131.
97	ZUO Yi, LIU Min, GUO Xinwen. Recent advances in synthesis and catalytic oxidation reactions of titanium silicates[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2015, 31(2): 343-359.
98	INAGAKI S, TSUBOI Y, SASAKI M, et al. Enhancement of para-selectivity in the phenol oxidation with H₂O₂ over Ti-MCM-68 zeolite catalyst[J]. Green Chemistry, 2016, 18(3): 735-741.
99	ZHANG Shengxiang, NISHI Yuko, NAKAMURA Kaisei, et al. Efficient synthesis of MSE-type zeolite using a highly effective organic structure-directing agent and excellent catalytic performance of its derived titanosilicate[J]. Microporous and Mesoporous Materials, 2025, 384: 113452.
100	SERRANO D P, SANZ R, PIZARRO P, et al. Hierarchical TS-1 zeolite as an efficient catalyst for oxidative desulphurization of hydrocarbon fractions[J]. Applied Catalysis B: Environmental, 2014, 146: 35-42.
101	ZHANG Jiani, BAI Risheng, FENG Zhaochi, et al. Amide-assisted synthesis of TS-1 zeolites with active Ti(OH₂)₂(OH)₂(OSi)₂ sites toward efficient oxidative desulfurization[J]. Applied Catalysis B: Environmental, 2024, 342: 123339.
102	Yoshihiro KON, YOKOI Toshiyuki, YOSHIOKA Masato, et al. Selective hydrogen peroxide oxidation of sulfides to sulfoxides or sulfones with MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions[J]. Tetrahedron, 2014, 70(41): 7584-7592.
103	史春风, 林民, 朱斌, 等. 空心钛硅分子筛在二甲基硫醚液相氧化反应中的催化性能[J]. 石油学报(石油加工), 2018, 34(4): 805-810.
	SHI Chunfeng, LIN Min, ZHU Bin, et al. Catalytic peformance of hollow titanosilicate zeolite in dimethyl sulfide liquid phase oxidation reaction[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2018, 34(4): 805-810.
104	Iveta MARTAUSOVÁ, Daniela SPUSTOVÁ, CVEJN Daniel, et al. Catalytic activity of advanced titanosilicate zeolites in hydrogen peroxide S-oxidation of methyl(phenyl)sulfide[J]. Catalysis Today, 2019, 324: 144-153.
105	ROBINSON Denis J, MCMORN Paul, BETHELL Donald, et al. N-oxidation of pyridines by hydrogen peroxide in the presence of TS-1[J]. Catalysis Letters, 2001, 72(3): 233-234.
106	XIE Wei, ZHENG Yuting, ZHAO Song, et al. Selective oxidation of pyridine to pyridine-N-oxide with hydrogen peroxide over Ti-MWW catalyst[J]. Catalysis Today, 2010, 157(1/2/3/4): 114-118.
54	WANG Lingling, WANG Yong, LIU Yueming, et al. Post-transformation of MWW-type lamellar precursors into MCM-56 analogues[J]. Microporous and Mesoporous Materials, 2008, 113(1/2/3): 435-444.
55	WANG Tao, JIN Fang, YI Xianfeng, et al. Atom-planting synthesis of MCM-36 catalyst to investigate the influence of pore structure and titanium coordination state on epoxidation activity[J]. Microporous and Mesoporous Materials, 2021, 310: 110645.
56	TANG Zhimou, YU Yunkai, CHEN Zhen, et al. Expanded titanosilicate MWW-related materials synthesized from a boron-containing precursor as an efficient catalyst for cyclohexene oxidation[J]. Microporous and Mesoporous Materials, 2021, 327: 111437.
57	JIN Shaoqing, TAO Guiju, ZHANG Shilin, et al. A facile organosilane-based strategy for direct synthesis of thin MWW-type titanosilicate with high catalytic oxidation performance[J]. Catalysis Science & Technology, 2018, 8(23): 6076-6083.
58	NA Kyungsu, Changbum JO, KIM Jaeheon, et al. MFI titanosilicate nanosheets with single-unit-cell thickness as an oxidation catalyst using peroxides[J]. ACS Catalysis, 2011, 1(8): 901-907.
59	VAN DER WAAL J C, RIGUTTO M S, VAN BEKKUM H. Zeolite titanium beta as a selective catalyst in the epoxidation of bulky alkenes[J]. Applied Catalysis A: General, 1998, 167(2): 331-342.
60	TANG Bo, DAI Weili, SUN Xiaoming, et al. A procedure for the preparation of Ti-Beta zeolites for catalytic epoxidation with hydrogen peroxide[J]. Green Chemistry, 2014, 16(4): 2281-2291.
61	LIN Haoyi, WANG Jiaqi, GAO Boxin, et al. Solvent-free and low template content synthesis of Ti-Beta zeolite via interzeolite transformation for oxidative desulfurization[J]. Microporous and Mesoporous Materials, 2022, 344: 112203.
62	WU Peng, KOMATSU Takayuki, YASHIMA Tatsuaki. Ammoximation of ketones over titanium mordenite[J]. Journal of Catalysis, 1997, 168(2): 400-411.
63	XU Hao, ZHANG Yingtian, WU Haihong, et al. Postsynthesis of mesoporous MOR-type titanosilicate and its unique catalytic properties in liquid-phase oxidations[J]. Journal of Catalysis, 2011, 281(2): 263-272.
64	PENG Rusi, WAN Zhipeng, LV Huanzhi, et al. Al-Modified Ti-MOR as a robust catalyst for cyclohexanone ammoximation with enhanced anti-corrosion performance[J]. Catalysis Science & Technology, 2021, 11(22): 7287-7299.
65	KUBOTA Yoshihiro, KOYAMA Yoshihito, YAMADA Taku, et al. Synthesis and catalytic performance of Ti-MCM-68 for effective oxidation reactions[J]. Chemical Communications, 2008(46): 6224-6226.
66	YIN Jianyong, LU Xinqing, YAN Jiayin, et al. Postsynthesis of Ti-UZM-35 titanosilicate as efficient catalyst for phenol hydroxylation reaction[J]. Microporous and Mesoporous Materials, 2020, 305: 110321.
67	INAGAKI Satoshi, KANEDA Midori, HAIKAL Danial, et al. Crystallization behavior of highly defective MSE-type zeolite, incorporation of Ti into the framework, and its hydrophobic-hydrophilic nature controlled by post-synthesis modifications[J]. Crystal Growth & Design, 2023, 23(5): 3681-3693.
68	金少青, 孙洪敏, 杨为民. 沸石分子筛催化剂在化学工业中的应用[J]. 高等学校化学学报, 2021, 42(1): 217-226.
	JIN Shaoqing, SUN Hongmin, YANG Weimin. Applications of zeolite catalysts in chemical industry[J]. Chemical Journal of Chinese Universities, 2021, 42(1): 217-226.
69	WU Peng, KOMATSU Takayuki, YASHIMA Tatsuaki. Characterization of titanium species incorporated into dealuminated mordenites by means of IR spectroscopy and ¹⁸O-exchange technique[J]. The Journal of Physical Chemistry, 1996, 100(24): 10316-10322.
70	XU Le, DING Jianghong, YANG Yulin, et al. Distinctions of hydroxylamine formation and decomposition in cyclohexanone ammoximation over microporous titanosilicates[J]. Journal of Catalysis, 2014, 309: 1-10.
71	LU Xinqing, GUAN Yejun, XU Hao, et al. Clean synthesis of furfural oxime through liquid-phase ammoximation of furfural over titanosilicate catalysts[J]. Green Chemistry, 2017, 19(20): 4871-4878.
72	WAN Zhipeng, TAN Jingyi, CHEN Wei, et al. MOR-type titanosilicate with specific Ti location in defective T3 sites for efficient cyclohexanone ammoximation[J]. ACS Catalysis, 2024, 14(13): 10102-10112.
73	PENG Rusi, PAN Huang, LI Xintong, et al. Post-synthesis of MSE-type titanosilicates by interzeolite transformation for selective anisole hydroxylation[J]. Catalysis Science & Technology, 2022, 12(20): 6098-6111.
74	BLASCO T, CORMA A, NAVARRO M T, et al. Synthesis, characterization, and catalytic activity of Ti-MCM-41 structures[J]. Journal of Catalysis, 1995, 156(1): 65-74.
75	WU Peng, TATSUMI Takashi, KOMATSU Takayuki, et al. Postsynthesis, characterization, and catalytic properties in alkene epoxidation of hydrothermally stable mesoporous Ti-SBA-15[J]. Chemistry of Materials, 2002, 14(4): 1657-1664.
76	李学峰, 高焕新, 金国杰, 等. 硅烷化对Ti/HMS分子筛催化性能的影响[J]. 催化学报, 2007, 28(6): 551-556.
	LI Xuefeng, GAO Huanxin, JIN Guojie, et al. Influence of silylation on catalytic performance of Ti/HMS molecular sieve[J]. Chinese Journal of Catalysis, 2007, 28(6): 551-556.
77	雷世龙. 丙烯环氧化工艺概述及催化剂研究进展[J]. 石油化工, 2024, 53(3): 410-417.
	LEI Shilong. Overview of propylene epoxidation process and research advances in epoxidation catalysts[J]. Petrochemical Technology, 2024, 53(3): 410-417.
78	于剑昆, 李中, 刘青炜. BASF-Dow公司HPPO工艺介绍[J]. 化学推进剂与高分子材料, 2011, 9(5): 8-23.
	YU Jiankun, LI Zhong, LIU Qingwei. Introduction of BASF-dow corporation’s HPPO process[J]. Chemical Propellants & Polymeric Materials, 2011, 9(5): 8-23.
79	于剑昆. Degussa-Uhde公司的HPPO工艺介绍[J]. 化学推进剂与高分子材料, 2009, 7(2): 15-22, 30.
	YU Jiankun. Introduction of degussa-uhde HPPO process[J]. Chemical Propellants & Polymeric Materials, 2009, 7(2): 15-22, 30.
80	YIN Jinpeng, JIN Xin, XU Hao, et al. Structured binder-free MWW-type titanosilicate with Si-rich shell for selective and durable propylene epoxidation[J]. Chinese Journal of Catalysis, 2021, 42(9): 1561-1575.
81	YU Yunkai, WANG Jianhao, FANG Nan, et al. Evidence of solvent-mediated proton transfer during H₂O₂ activation in titanosilicate-catalyzed oxidation systems[J]. Physical Chemistry Chemical Physics, 2023, 25(17): 12220-12230.
82	YU Yunkai, FANG Nan, CHEN Zhen, et al. Greening oxidation catalysis: Water as a solvent for efficient alkene epoxidation over a titanosilicate/H₂O₂ system[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(35): 11641-11654.
83	TANG Kang, HOU Weilong, WANG Xiaoshu, et al. Enhanced catalytic performance of trimethylsilylated Ti-MWW zeolites for the liquid-phase epoxidation of propylene with H₂O₂ [J]. Microporous and Mesoporous Materials, 2021, 328: 111492.
84	LIU Dongxu, WANG Rui, YU Yunkai, et al. Chemical deactivation of titanosilicate catalysts caused by propylene oxide in the HPPO process[J]. Catalysis Science & Technology, 2023, 13(5): 1437-1447.
85	于剑昆, 吕国会. 国内HPPO工业化技术进展[J]. 化学推进剂与高分子材料, 2019, 17(1): 1-16.
	YU Jiankun, Guohui LYU. Progress of domestic HPPO industrialized technology[J]. Chemical Propellants & Polymeric Materials, 2019, 17(1): 1-16.
86	于剑昆, 张会君, 沈冲. 国内HPPO工业化技术近况(续前)[J]. 化学推进剂与高分子材料, 2020, 18(2): 10-23.
	YU Jiankun, ZHANG Huijun, SHEN Chong. Recent situation of domestic HPPO industrialization techniqu(Contn.)[J]. Chemical Propellants & Polymeric Materials, 2020, 18(2): 10-23.
87	夏长久, 于佳元, 林民, 等. 中国石化双氧水法制环氧丙烷工业开发及关键科技问题[J]. 石油炼制与化工, 2024, 55(1): 130-134.
	XIA Changjiu, YU Jiayuan, LIN Min, et al. Key scientific problems and industrial development of Sinopec hppo technology for green propylene oxide production[J]. Petroleum Processing and Petrochemicals, 2024, 55(1): 130-134.
88	于剑昆. 近年来国内CHPPO工业化技术最新进展(待续)[J]. 化学推进剂与高分子材料, 2023, 21(4): 17-31.
	YU Jiankun. Latest progress of domestic CHPPO industrialization technique in recent years(Cont.)[J]. Chemical Propellants & Polymeric Materials, 2023, 21(4): 17-31.
89	于剑昆. 近年来国内CHPPO工业化技术最新进展(续前)[J]. 化学推进剂与高分子材料, 2023, 21(5): 28-41.
	YU Jiankun. Latest progress of domestic CHPPO industrialization technique in recent years(contn.)[J]. Chemical Propellants & Polymeric Materials, 2023, 21(5): 28-41.
90	于剑昆. 近年来国内CHPPO工业化技术最新进展(续完)[J]. 化学推进剂与高分子材料, 2023, 21(6): 10-25.
	YU Jiankun. Latest progress of domestic CHPPO industrialization technique in recent years(to the end)[J]. Chemical Propellants & Polymeric Materials, 2023, 21(6):10-25.

[1]	GUO Pei, CUI Cancan, KONG Dejie, HUANG Sheng. Development trend of sulfide solid electrolytes for solid-state lithium batteries in the context of “dual carbon goals” [J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5193-5206.
[2]	SHI Jiating, WANG Hui, PU Kaikai, ZHAO Ting, NIE Lijun, ZHENG Na, GAO Yuhang, XUE Kunkun, SHI Jianhui. Enhanced hydrogen peroxide production performance in visible light from ultra-thin g-C₃N₄ nanosheets with carbon vacancies [J]. Chemical Industry and Engineering Progress, 2024, 43(7): 4148-4154.
[3]	ZHANG Changsheng, WEN Song, ZHAO Jinchong, LU Fangxu, JIANG Jie. Advances in chemical deoxidation of oxygen-containing organic gases in chemical processes [J]. Chemical Industry and Engineering Progress, 2024, 43(2): 903-912.
[4]	XU Qin, WANG Baoguo. Recent progress on carbon-based electrocatalysts for hydrogen peroxide production via two-electron oxygen reduction reaction [J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6155-6172.
[5]	YANG Jianping. PSE for feedstock consumption reduction in reaction system of HPPO plant [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 21-32.
[6]	MAO Shanjun, WANG Zhe, WANG Yong. Group recognition hydrogenation: From concept to application [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3917-3922.
[7]	ZHANG Peng, PAN Yuan. Progress of single atom catalysts in electrocatalytic oxygen reduction to hydrogen peroxide [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2944-2953.
[8]	JIN Yong, CHENG Yi, BAI Dingrong, ZHANG Chenxi, WEI Fei. Fluidization research and development in China [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2761-2780.
[9]	SONG Wangyi, ZHAO Xinfang, LIU Wei, XUE Ling. Effect of valve hardening process on hydrogen peroxide production by anthraquinone process [J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 54-59.
[10]	LIAO Bing, XU Wen, YE Qiuyue. A review of activated percarbonate and peroxymonocarbonate in the field of water treatment [J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3235-3248.
[11]	SHAO Bin, SUN Zheyi, ZHANG Yun, PAN Fenghongkang, ZHAO Kaiqing, HU Jun, LIU Honglai. Recent progresses in CO₂ to syngas and high value-added products [J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1136-1151.
[12]	XIAO Boren, YANG Jinxing, LIU Haipeng, QI Lihong, ZUO Guomin. Application of the catalysis and activation system based on hydrogen peroxide on the decontamination of hazardous chemicals [J]. Chemical Industry and Engineering Progress, 2021, 40(S1): 426-433.
[13]	SHI Yanqiang, XIA Yuetong, WEN Langyou, GAO Liang, XU Guangtong, ZONG Baoning. Hydrogen peroxide and its green synthesis of basic organic chemicals [J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2048-2059.
[14]	LIANG Hairui, WANG Li, LIU Guozhu. A review of recent development on catalysts for direct synthesis of hydrogen peroxide from hydrogen and oxygen [J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2060-2069.
[15]	FAN Tao. Industrial application progress of lignite pyrolysis technology in eastern area of Inner Mongolia, China [J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1362-1370.