摘要
联环己烷是一种高储氢密度、低沸点储氢试剂。与联苯加氢相比,苯和环己烯烷基化制环己基苯再加氢是一种有望实现大规模制备联环己烷的途径。在成熟的烷基化技术基础上,需进一步开展高效环己基苯加氢催化剂的研发。本研究首先使用酸化的USY分子筛催化苯和环己烯烷基化至环己基苯,获得100%转化率和产物选择性。进一步通过原子层沉积(ALD)在γ-Al_(2)O_(3)表面预先沉积不同厚度的TiO_(2)膜后再负载铂颗粒制得Pt/TiO_(2)/γ-Al_(2)O_(3)催化剂,研究TiO_(2)膜提升催化剂环己基苯加氢性能机制。TEM、CO脉冲吸附、CO-DRIFTs、准原位XPS、H-D交换和H2-TPR表征显示,与Pt/γ-Al_(2)O_(3)相比,Pt/TiO_(2)/γ-Al_(2)O_(3)催化剂不改变Pt颗粒的分散度,但能够形成新的Pt-TiO_(2)相互作用,提高铂表面电子密度、平面活性位点比例和降低氢溢流能垒,提升环己烷基苯加氢性能。研究为进一步发展联环己烷有机液态储氢试剂提供理论支持。相关金属-载体相互作用调控策略可应用于其他芳香性分子高效加氢催化剂的研制。
Bicyclohexane is a hydrogen storage reagent with high hydrogen density and low boiling point.Compared with the hydrogenation of biphenyl,the alkylation of benzene and cyclohexene to cyclohexylbenzene and hydrogenation is a promising way to prepare cyclohexane on a large scale.The research and development of highefficiency cyclohexyl benzene hydrogenation catalyst should be further developed based on mature alkylation technology.This paper used an acidified USY molecular sieve to catalyze the alkylation of benzene and cyclohexene to cyclohexylbenzene,which achieved 100%conversion and selectivity.Furthermore,Pt/TiO_(2)/γ-Al_(2)O_(3) catalyst is prepared by pre-deposition TiO_(2) film of different thicknesses onγ-Al_(2)O_(3) surface and then supported with platinum particles by Atomic layer deposition(ALD).The role of TiO_(2) film in improving the cyclohexylbenzene hydrogenation performance of the catalyst is studied.TEM,CO pulse chemisorption,CO-DRIFTs,quasi-in situ XPS,H-D exchange,and H2-TPR characterization show that compared with Pt/γ-Al_(2)O_(3),TiO_(2) thin films on Pt/TiO_(2)/γ-Al_(2)O_(3) do not change the dispersion of Pt particles,but can form new Pt-TiO_(2) interactions.The hydrogenation performance of cyclohexylbenzene was improved by increasing the electron density and the proportion of planar active sites on the surface of platinum and reducing the energy barrier of hydrogen spillover.The research provides theoretical support for further bicyclohexane organic liquid hydrogen storage reagent development.The relevant metal-support interaction regulation strategy can be applied to the development of efficient catalysts for other aromatic molecules hydrogenation.
作者
刘瑞林
王森
孟繁春
李卓
杨慧敏
赵世超
覃勇
张斌
LIU Ruilin;WANG Sen;MENG Fanchun;LI Zhuo;YANG Huimin;ZHAO Shichao;QIN Yong;ZHANG Bin(State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China;University of Chinese Academy of Sciences,Beijing 100049,China)
出处
《燃料化学学报（中英文）》
EI
CAS
CSCD
北大核心
2024年第9期1290-1298,共9页
Journal of Fuel Chemistry and Technology
基金
国家自然科学基金(22072172,22202227)
国家杰出青年科学基金(21825204)
中国科学院青年创新促进会(Y2021056)
榆林学院与大连清洁能源国家实验室合作基金(YLU-DNL Fund 2022007)
山西省科技创新团队专项资金(202304051001007)资助。
关键词
有机液态储氢
联环己烷
加氢
金属载体相互作用
原子层沉积
organic liquid hydrogen storage
bicyclohexane
hydrogenation
metal-support interaction
atomic layer deposition
