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

doi:10.11949/0438-1157.20250164

Abstract

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

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

CLC Number:

TQ 032.4

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.

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.

Figures/Tables 10

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

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

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

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

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

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

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

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

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

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

References 32

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

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

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