ZnO/WO3异质结光催化环烯烃［2+2］环加成制备高能量密度燃料

doi:10.11949/0438-1157.20250164

化工学报 ›› 2025, Vol. 76 ›› Issue (9): 4882-4892.DOI: 10.11949/0438-1157.20250164

ZnO/WO₃异质结光催化环烯烃［2+2］环加成制备高能量密度燃料

佟丽丽¹(), 陈英¹^,²(), 艾敏华¹(), 舒玉美¹, 张香文¹, 邹吉军¹, 潘伦¹()

^1.天津大学化工学院，天津大学国家储能技术产教融合创新平台，储能科学与工程研究院，先进燃料与化学推进剂教育部重点实验室，天津 300350
^2.烟台大学化学化工学院，山东烟台 264005

收稿日期:2025-02-21 修回日期:2025-05-13 出版日期:2025-09-25 发布日期:2025-10-23
通讯作者: 艾敏华,潘伦
作者简介:佟丽丽（1983—），女，博士研究生，1060207133@qq.com
陈英（1991—），女，博士，讲师，chen0915@ytu.edu.cn
基金资助:
航空科学基金项目(2023Z073048003);国家自然科学基金项目(22408272);国家自然科学基金项目(22222808);国家自然科学基金项目(U24A20547)

ZnO/WO₃ heterojunction modulated [2+2] photocycloaddition of cycloolefins for high-energy-density fuels production

Lili TONG¹(), Ying CHEN¹^,²(), Minhua AI¹(), Yumei SHU¹, Xiangwen ZHANG¹, Jijun ZOU¹, Lun PAN¹()

^1.School of Chemical Engineering and Technology, National Industry-Education Platform for Energy Storage, Institute of Energy Storage Science and Engineering, Key Laboratory for Advanced Fuel and Chemical Propellant of Ministry of Education, Tianjin University, Tianjin 300350, China
^2.School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, Shandong, China

Received:2025-02-21 Revised:2025-05-13 Online:2025-09-25 Published:2025-10-23
Contact: Minhua AI, Lun PAN

摘要/Abstract

摘要：

高能量密度燃料作为航空推进系统的关键能源，可通过分子结构设计与组成优化提高飞行器的航程、航速和载荷能力。光化学为张力结构燃料和多环结构燃料合成提供了一种绿色工艺，但面临光生电荷分离效率低、反应性能差等问题。本工作研究了ZnO/WO₃异质结光催化降冰片二烯和环己烯酮混合体系的［2+2］环加成过程。通过反应路径调控实现了混合燃料组成调制，有效解决了单组分燃料中密度和冰点性能的制约限制。研究发现，在光催化剂催化和环己烯酮敏化作用下，降冰片二烯分子内环加成制备四环庚烷的反应过程被促进。相比于ZnO，ZnO/WO₃异质结光催化剂会抑制激发三重态环己烯酮的形成，进而抑制环己烯酮参与的分子间［2+2］环加成反应过程。最终通过加氢脱氧精制获得混合燃料产品，其中QC/1-adduct质量比约为1.20时，其密度为0.984 g/cm³，热值为43.17 MJ/kg，冰点<-60℃。本工作为开发高效和可持续的航空能源体系提供了新思路。

关键词: 光化学, ［2+2］环加成, 高能量密度航空燃料, 异质结光催化剂, 环烯烃, 燃料, 可持续性

Abstract:

High energy density fuel is the core energy of aviation propulsion system, and the molecular structure design and composition optimization of fuel can significantly improve the range, load capacity and overall performance of aircraft. Photochemistry provides a green process for the synthesis of tensile structure fuels and multi-ring structure fuels, but it faces problems such as low efficiency of photogenerated charge separation and poor reaction performance. In this work, the photocatalytic [2+2] cycloaddition of norbornadiene and cyclohexenone mixed system was studied. The multi-component mixed fuel was synthesized by adjusting the reaction path to balance the contradiction between fuel density and freezing point. The synthesis of tetracycloheptane via intramolecular photocycloaddition of norbornadiene is promoted by photocatalysts and cyclohexenone sensitization. Compared with ZnO, ZnO/WO₃ heterojunction photocatalyst inhibits the formation of excited triplet cyclohexenone, and then inhibits the intermolecular [2+2] cycloaddition reaction process involving cyclohexenone. The fuels with different components are obtained through hydrodeoxygenation refining. When the mass ratio of QC/1-adduct in the blending fuel is about. 1.20, its density is 0.984 g/cm³, the calorific value is 43.17 MJ/kg, and the freezing point is <-60℃. This work provides new ideas for the development of an efficient and sustainable aviation energy system.

Key words: photochemistry, [2+2] cycloaddition, high-energy-density fuels, heterojunction photocatalyst, cycloolefins, fuel, sustainability

中图分类号:

TQ 032.4

佟丽丽, 陈英, 艾敏华, 舒玉美, 张香文, 邹吉军, 潘伦. ZnO/WO₃异质结光催化环烯烃［2+2］环加成制备高能量密度燃料[J]. 化工学报, 2025, 76(9): 4882-4892.

Lili TONG, Ying CHEN, Minhua AI, Yumei SHU, Xiangwen ZHANG, Jijun ZOU, Lun PAN. ZnO/WO₃ heterojunction modulated [2+2] photocycloaddition of cycloolefins for high-energy-density fuels production[J]. CIESC Journal, 2025, 76(9): 4882-4892.

图/表 10

图1 混合环烯烃[2+2]光环加成合成高能量密度燃料

Fig. 1 The process of high-density fuels through [2+2] photocycloaddition of mixed cycloolefins

图2 ZnO、ZnO/WO3和WO3的XRD谱图（a）和紫外-可见漫反射光谱（b）；NBD（c）和CHOE（d）分别加入ZnO和ZnO/WO3异质结前后的紫外-可见吸收光谱

Fig.2 XRD patterns (a) and UV-vis diffuse reflection spectra (b) of ZnO, ZnO/WO3 and WO3; UV-vis absorption spectra of NBD (c) and CHOE (d) before and after the addition of ZnO and ZnO/WO3 heterojunction, respectively

图3 CHOE及加入ZnO或ZnO/WO3异质结的磷光光谱（77 K）（a）和磷光寿命（b）；（c）ZnO和ZnO/WO3异质结加入CHOE和CHOE-NBD混合体系的磷光信号强度（458 nm）；（d）加入CHOE前后ZnO/WO3异质结的荧光光谱

Fig. 3 Phosphorescence (PH) spectra (77 K) (a) and phosphorescence lifetime (b) of CHOE with or without ZnO and ZnO/WO3 heterojunction; (c) The phosphorescence signal intensity of CHOE and CHOE-NBD with the addition of ZnO and ZnO/WO3 heterojunctions at 458 nm; (d) Steady-state photoluminescence (PL) spectra of ZnO/WO3 heterojunction with or without CHOE

图4 （a）产物色谱图；（b）NBD和CHOE光催化[2+2]环加成反应随时间的变化

Fig. 4 (a) GC spectra of products distribution; (b) Time-dependent [2+2] photocycloaddition of NBD and CHOE

图5 ZnO与ZnO/WO3异质结对纯NBD体系（a）和纯CHOE体系（b）光环加成反应过程的影响

Fig. 5 The effects of ZnO and ZnO/WO3 heterojunction on photocycloaddition process of NBD (a) or CHOE(b)

图6 催化剂（a）和ZnO/WO3异质结用量（b）对CHOE和NBD光催化[2+2]环加成的影响

Fig. 6 Effects of catalysts (a) and the amount of ZnO/WO3 heterojunction (b) on the [2+2] photocycloaddition of NBD and CHOE

图7 反应温度（a）和光强（b）对光催化[2+2]环加成反应的影响作用；（c）ZnO/WO3异质结的循环稳定性测试

Fig. 7 Effects of temperature (a) and light intensity (b) on [2+2] photocycloaddition; (c) Stability test of ZnO/WO3 heterojunctions

图8 （a） ZnO和ZnO/WO3异质结对CHOE与QC光催化[2+2]环加成反应的影响；（b）SiO2对CHOE与NBD的[2+2]光环加成反应的影响

Fig. 8 (a) Effect of ZnO and ZnO/WO3 heterojunction on the [2+2] photocycloaddition of CHOE and QC; (b)Effect of SiO2 on the [2+2] photocycloaddition of NBD and CHOE

图9 ZnO/WO3异质结光催化环烯烃[2+2]环加成反应路径

Fig. 9 Proposed pathway of [2+2] photocycloaddition of cycloolefins catalyzed by ZnO/WO3 heterojunction

表1 QC、1-adduct以及不同催化条件下得到的混合燃料的性质

Table 1 Properties of QC， 1-adduct and blending fuels obtained under different catalytic conditions

Fuel	Catalysts	Density (20℃)/(g/cm³)	NHOC/(MJ/kg)	Viscosity (-20℃)/(mm²/s)	Freezing point/℃
QC	—	0.982	44.38	1.92	-44
1-adduct	—	0.986	41.72	41.68	<-65
QC/1-adduct (57%(mass))	—	0.985	42.58	8.25	<-60
QC/1-adduct (60%(mass))	ZnO	0.985	42.60	8.04	<-60
QC/1-adduct (83%(mass))	ZnO/WO₃ (2.5 mg)	0.984	42.89	6.16	<-60
QC/1-adduct (120%(mass))	ZnO/WO₃ (5.0 mg)	0.984	43.17	5.07	<-60
QC/1-adduct (172%(mass))	ZnO/WO₃ (40.0 mg)	0.983	43.48	4.09	<-60

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ZnO/WO₃异质结光催化环烯烃［2+2］环加成制备高能量密度燃料

ZnO/WO₃ heterojunction modulated [2+2] photocycloaddition of cycloolefins for high-energy-density fuels production

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