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使用阮内镍通过光热催化将乙酰丙酸转化为γ-戊内酯时的能量需求最小化

Minimizing Energy Demand in the Conversion of Levulinic Acid to γ‑Valerolactone via Photothermal Catalysis Using Raney Ni.

作者信息

Bujaldón Roger, Fons Arnau, Garcia-Amorós Jaume, Vaca Cristina, Nogués Josep, Esplandiu Maria José, Gómez Elvira, Sepúlveda Borja, Serrà Albert

机构信息

Grup d'Electrodeposició de Capes Primes i Nanoestructures (GE-CPN), Departament de Ciència de Materials i Química Física, Universitat de Barcelona, Martí i Franquès, 1, Barcelona, Catalonia, E-08028, Spain.

Institute of Nanoscience and Nanotechnology (IN2UB), Universitat de Barcelona, Barcelona, Catalonia, Spain.

出版信息

Adv Sci (Weinh). 2025 Jun;12(21):e2416153. doi: 10.1002/advs.202416153. Epub 2025 Apr 17.

DOI:10.1002/advs.202416153
PMID:40245161
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12140316/
Abstract

The valorization of lignocellulosic wastes emerges as a prime strategy to mitigate the global carbon footprint. Among the multiple biomass derivatives, γ-valerolactone is particularly attractive as precursor of high-value chemicals, biofuel, green solvent or perfumery. γ-Valerolactone can be synthesized through a hydrogenation reaction from levulinic acid, obtained from cellulose. However, the high energy requirements of this synthetic pathway have hindered its industrial viability. To drastically reduce the reaction energy requirements, here a novel synthetic strategy, based on solvothermal-photothermal processes using cost-effective Raney-Ni as photothermal catalyst, is proposed. First, the use of hydrogen gas is avoided by selecting isopropanol as a safer and greener H-source. Second, a photothermocatalytic process is used to minimize the reaction temperature and time with respect to conventional reactions. This approach exploits the broadband optical absorption of the Raney®-Ni, due to its highly damped plasmonic behavior, to achieve fast and efficient catalyst heating inside the reactor. The photothermal reaction required less than 2 h and just 132 °C to reach over 95% conversion, thereby drastically reducing the reaction time and energy consumption compared to conventional reactions. Importantly, these conditions granted high catalyst reusability. This solvothermal-photothermal approach could offer a sustainable alternative for the industrial production of γ-valerolactone.

摘要

木质纤维素废料的增值成为减轻全球碳足迹的首要策略。在多种生物质衍生物中,γ-戊内酯作为高价值化学品、生物燃料、绿色溶剂或香料的前体特别具有吸引力。γ-戊内酯可通过纤维素制得的乙酰丙酸经氢化反应合成。然而,这种合成途径的高能量需求阻碍了其工业可行性。为大幅降低反应能量需求,本文提出一种基于使用具有成本效益的雷尼镍作为光热催化剂的溶剂热-光热过程的新型合成策略。首先,通过选择异丙醇作为更安全、更环保的氢源避免使用氢气。其次,使用光热催化过程相对于传统反应将反应温度和时间降至最低。这种方法利用雷尼镍由于其高度阻尼的等离子体行为而具有的宽带光吸收,在反应器内实现快速高效的催化剂加热。光热反应只需不到2小时且仅在132°C就能达到超过95%的转化率,从而与传统反应相比大幅减少了反应时间和能耗。重要的是,这些条件赋予了催化剂高可重复使用性。这种溶剂热-光热方法可为γ-戊内酯的工业生产提供一种可持续的替代方案。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/cdeda120a864/ADVS-12-2416153-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/34f86e7cbda1/ADVS-12-2416153-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/9f82ba5f065e/ADVS-12-2416153-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/60d7e7de302f/ADVS-12-2416153-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/b72e5306da1b/ADVS-12-2416153-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/cdeda120a864/ADVS-12-2416153-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/34f86e7cbda1/ADVS-12-2416153-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/9f82ba5f065e/ADVS-12-2416153-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/60d7e7de302f/ADVS-12-2416153-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/b72e5306da1b/ADVS-12-2416153-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c33e/12140316/cdeda120a864/ADVS-12-2416153-g001.jpg

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本文引用的文献

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Advances in Sustainable γ-Valerolactone (GVL) Production via Catalytic Transfer Hydrogenation of Levulinic Acid and Its Esters.通过乙酰丙酸及其酯的催化转移氢化实现可持续γ-戊内酯(GVL)生产的进展
ACS Sustain Chem Eng. 2024 Sep 30;12(45):16494-16517. doi: 10.1021/acssuschemeng.4c05812. eCollection 2024 Nov 11.
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Enhancing reductive conversion of levulinic acid and levulinates to γ-valerolactone: Role of oxygen vacancy in MnOx catalysts.增强乙酰丙酸和乙酰丙酸盐还原转化为γ-戊内酯:MnO x 催化剂中氧空位的作用。
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Modeling and Thermodynamic Studies of γ-Valerolactone Production from Bio-derived Methyl Levulinate.
生物基乙酰丙酸甲酯制备γ-戊内酯的建模与热力学研究
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