Direct Reduction-Driven Active Species Formation in RuMn-Containing Zeolite Catalyst for 5-Hydroxymethylfurfural Oxidation

IF 3.2 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - An Asian Journal Pub Date : 2026-10-25 DOI:10.1002/asia.71021

Rahul Gautam, Rupinder Kaur, Nidhi Gossai, Kanika Saini, Cheralathan Kanakkampalayam Krishnan, Shunmugavel Saravanamurugan

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Abstract

The selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is an important transformation for producing sustainable bio-based chemicals and polymer precursors. Here, the influence of pretreatment strategies on the physicochemical properties and catalytic performance of RuMn supported on modified H-ZSM-5 (RuMn/ZS) was investigated for HMF oxidation. Directly reduced RuMn/ZS (RuMn/ZS-R) was compared with calcined RuMn/ZS (RuMn/ZS-C) and calcined-reduced RuMn/ZS (RuMn/ZS-CR). RuMn/ZS-R exhibited the highest activity, affording 72.7% FDCA yield and 75.7% total furanics yield, compared with 5.0% and 14.1% FDCA for RuMn/ZS-C and RuMn/ZS-CR, respectively. XPS and TEM analyses revealed that direct reduction promotes highly dispersed metallic Ru⁰ species together with Mn³⁺/Mn⁴⁺ promoter species. NH₃-TPD, CO₂-TPD, and in situ diffuse reflectance infrared Fourier transform (DRIFTS) further demonstrated enhanced Lewis and Brønsted acidity and a higher concentration of moderate basic sites in RuMn/ZS-R. Poisoning experiments supported the contribution of both acidic and basic sites to HMF oxidation. The superior performance of RuMn/ZS-R is attributed to the synergistic interplay of highly dispersed Ru⁰, Mn promoter species, acidic sites, and moderate basic sites generated by direct reduction. These findings provide insight into designing multifunctional zeolite (ZS)-supported catalysts for selective biomass oxidation.

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5-羟甲基糠醛氧化催化剂中直接还原驱动活性物质的形成

5-羟甲基糠醛（HMF）选择性氧化生成2,5-呋喃二羧酸（FDCA）是生产可持续生物基化学品和聚合物前体的重要转化。本文研究了预处理策略对改性H-ZSM-5负载RuMn （RuMn/ZS）氧化HMF的理化性质和催化性能的影响。将直接还原的RuMn/ZS （RuMn/ZS- r）与煅烧的RuMn/ZS （RuMn/ZS- c）和煅烧还原的RuMn/ZS （RuMn/ZS- cr）进行比较。RuMn/ZS-R活性最高，FDCA产率为72.7%，总呋喃产率为75.7%，而RuMn/ZS-C和RuMn/ZS-CR的FDCA产率分别为5.0%和14.1%。XPS和TEM分析表明，直接还原促进了高度分散的金属Ru0和Mn3+/Mn4+启动子。NH3-TPD、CO2-TPD和原位漫反射红外傅里叶变换（DRIFTS）进一步表明，RuMn/ZS-R中的Lewis和Brønsted酸性增强，中等碱性位点浓度升高。中毒实验支持酸性和碱性位点对HMF氧化的贡献。RuMn/ZS-R的优异性能归因于高度分散的Ru0、Mn启动子、酸性位点和直接还原产生的中等碱性位点的协同作用。这些发现为设计多功能沸石（ZS）负载的选择性生物质氧化催化剂提供了新的思路。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemistry - An Asian Journal 化学-化学综合

CiteScore

7.00

自引率

2.40%

发文量

535

审稿时长

1.3 months

期刊介绍： Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).