木质素衍生的 4-甲基苯甲醚在温和条件下通过磷化钌纳米碳催化剂进行加氢脱氧反应

IF 6.7 1区 工程技术 Q2 ENERGY & FUELS Fuel Pub Date : 2024-11-12 DOI:10.1016/j.fuel.2024.133661
Sudhakar Pichaikaran, Zhongzheng Gao, Kai Li, Bo Wang
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引用次数: 0

摘要

以单宁酸为生物质碳源,采用水热法、碳化法和还原法原位合成了 (1:1)、(1:3) 和 (1:5) RuP@C-N 碳纳米球催化剂。使用多种仪器方法(包括 XRD)对合成材料进行了良好的描述,XRD 显示了磷化钌相的形成以及石墨碳。BET 表面积和 BJH 孔径分布显示材料具有多个中孔和微孔。XPS 测量评估了催化剂中碳纳米层和 RuP 之间的氧化态和键相互作用。FE-SEM 验证了材料的球形形态,而 EDS 图谱显示了 Ru、P、C、O 和 N 的存在。XPS 分析表明,催化剂中 C 和 N 的诱导影响了钌和磷之间的电子传输,从而产生了负责 C-O 键断裂的 Ruδ+/Pδ- 活性位点。此外,磷化钌在碳球中的高分散度和小粒径以及其酸性也对其高活性产生了重要影响。该研究以异丙醇为氢供体,在温和的反应条件下研究了 4-甲基苯甲醚的氢脱氧(HDO)反应。对于 (1:3) RuP@C-N 催化剂,4-甲基苯甲醚的最大转化率为 42.5%,甲苯选择性为 21.5%,TOF 为 45.35 h-1。(1:3) RuP@C-N 催化剂的活性最高,而高 P 浓度的 (1:5) RuP@C-N 催化剂对活性没有影响。脱甲基化/氢解是 4-甲基苯甲醚转化的最具选择性的反应途径。此外,该催化剂可连续再生和重复使用五次,并能保持其活性,没有明显的损失。
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Lignin-derived 4-methylanisole hydrodeoxygenation under mild conditions over ruthenium phosphide carbon nanosphere catalyst
(1:1), (1:3), and (1:5) RuP@C-N carbon nanosphere catalysts were synthesized by in situ method using a hydrothermal, carbonization, and reduction strategy with tannic acid as the biomass carbon source. The synthesized materials were well described using several instrumental methods, including XRD, which revealed ruthenium phosphide phase formation as well as graphitic carbon. BET surface area and BJH pore size distribution revealed that the materials had multiple meso and micropores. XPS measurements assess the oxidation states and bonding interaction between the carbon nanosphere and RuP in the catalyst. FE-SEM validates the material’s spherical morphology, whereas EDS mapping reveals the presence of Ru, P, C, O, and N. HR-TEM images reveal the high distribution of RuP particles on the carbon network. The induction of C and N in the catalyst impacted electron transport between ruthenium and phosphorus as evidenced by XPS analysis, leading to Ruδ+/Pδ- active sites responsible for C-O bond breakage. Additionally, the high dispersion and small particle size of ruthenium phosphide in the carbon spheres, as well as its acidity, had a significant impact on its high activity. The study investigated the hydrodeoxygenation (HDO) of 4-methylanisole under mild reaction conditions, with isopropanol as a hydrogen donor. The optimal conditions were 180 °C and 4 h, and for the (1:3) RuP@C-N catalyst, a maximum of 4-methylanisole conversion was 42.5 %, and a toluene selectivity of 21.5 % was reached at TOF 45.35 h−1. The (1:3) RuP@C-N catalyst was the most active, while the (1:5) RuP@C-N catalyst with a high P concentration had no added effect on activity. Demethylation/hydrogenolysis was the most selective reaction pathway for 4-methylanisole conversion. Furthermore, the catalyst was regenerated and reused for five consecutive runs, and maintained its activity without considerable loss.
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来源期刊
Fuel
Fuel 工程技术-工程:化工
CiteScore
12.80
自引率
20.30%
发文量
3506
审稿时长
64 days
期刊介绍: The exploration of energy sources remains a critical matter of study. For the past nine decades, fuel has consistently held the forefront in primary research efforts within the field of energy science. This area of investigation encompasses a wide range of subjects, with a particular emphasis on emerging concerns like environmental factors and pollution.
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