Tailoring the Acidity of Ru Supported on Sepiolite for Enhanced Catalytic Reductive Amination of Furfural to Furfurylamine

IF 3.9 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem Pub Date : 2025-08-24 DOI:10.1002/cctc.202500982

Kanika Saini, Supan, Neeraj Sharma, Rahul Gautam, Shunmugavel Saravanamurugan

{"title":"Tailoring the Acidity of Ru Supported on Sepiolite for Enhanced Catalytic Reductive Amination of Furfural to Furfurylamine","authors":"Kanika Saini,  Supan, Neeraj Sharma, Rahul Gautam, Shunmugavel Saravanamurugan","doi":"10.1002/cctc.202500982","DOIUrl":null,"url":null,"abstract":"The catalytic reductive amination of bio-based carbonyls has emerged as a promising route for producing N-containing compounds, having a wide range of applications in pharmaceuticals and agrochemicals. In this work, Ru supported on acid-treated sepiolite (Ru/ASep) is designed for the reductive amination of furfural (FUR) to furfurylamine (FUA) using H2 and NH3 as reductant and nitrogen source, respectively. Ru/ASep exhibited two times higher catalytic activity compared to its counterpart, that is, Ru supported on parent sepiolite (Ru/Sep), yielding 98.4% FUA. The NH3-temperature-programmed desorption (TPD) and NH3-diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy studies show that Ru/ASep exhibited an increase in total acidic sites with relatively more Lewis acidic sites than Ru/Sep, contributing to C═N bond activation and leading to the formation of FUA in high yield. The CO2-TPD results indicate that ASep possesses a large amount of basic sites, which contribute to a facile reduction of RuOx to Ru0 in Ru/ASep, as confirmed by H2-temperature programmed reduction (TPR) studies. H2-TPD studies indicate a higher amount of H2 activated over Ru/ASep, favoring the intermediate hydrogenation step to form FUA. Furthermore, the poisoning studies with KSCN indicated that Lewis acidic sites on the surface of Ru/ASep played a crucial role in the formation of FUA.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9000,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemCatChem","FirstCategoryId":"92","ListUrlMain":"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500982","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

Abstract

The catalytic reductive amination of bio-based carbonyls has emerged as a promising route for producing N-containing compounds, having a wide range of applications in pharmaceuticals and agrochemicals. In this work, Ru supported on acid-treated sepiolite (Ru/ASep) is designed for the reductive amination of furfural (FUR) to furfurylamine (FUA) using H₂ and NH₃ as reductant and nitrogen source, respectively. Ru/ASep exhibited two times higher catalytic activity compared to its counterpart, that is, Ru supported on parent sepiolite (Ru/Sep), yielding 98.4% FUA. The NH₃-temperature-programmed desorption (TPD) and NH₃-diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy studies show that Ru/ASep exhibited an increase in total acidic sites with relatively more Lewis acidic sites than Ru/Sep, contributing to C═N bond activation and leading to the formation of FUA in high yield. The CO₂-TPD results indicate that ASep possesses a large amount of basic sites, which contribute to a facile reduction of RuO_x to Ru⁰ in Ru/ASep, as confirmed by H₂-temperature programmed reduction (TPR) studies. H₂-TPD studies indicate a higher amount of H₂ activated over Ru/ASep, favoring the intermediate hydrogenation step to form FUA. Furthermore, the poisoning studies with KSCN indicated that Lewis acidic sites on the surface of Ru/ASep played a crucial role in the formation of FUA.

Abstract Image

查看原文本刊更多论文

调整海泡石负载钌的酸度以增强糠醛催化还原胺化制糠胺

生物基羰基催化还原胺化反应已成为生产含氮化合物的一种很有前途的途径，在制药和农用化学品中有着广泛的应用。本研究设计了Ru负载于酸处理海泡石（Ru/ASep）上，分别以H2和NH3为还原剂和氮源，将糠醛（FUR）还原胺化成糠胺（FUA）。Ru/ASep的催化活性是其载体海泡石（Ru/Sep）的2倍，FUA产率为98.4%。nh3 -程序升温解吸（TPD）和nh3 -弥反射红外傅里叶变换（DRIFT）光谱研究表明，Ru/ASep比Ru/Sep表现出总酸位点的增加和相对较多的Lewis酸位点，有助于C = N键的激活，并导致高收率的FUA的形成。CO2-TPD结果表明，ASep具有大量的碱性位点，这有助于Ru/ASep中RuOx易于还原为Ru0，这一点得到了h2 -温度程序还原（TPR）研究的证实。H2- tpd研究表明，Ru/ASep上的H2活化量较高，有利于中间加氢步骤形成FUA。此外，KSCN的中毒研究表明Ru/ASep表面的Lewis酸位点在FUA的形成中起着至关重要的作用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

ChemCatChem 化学-物理化学

CiteScore

8.10

自引率

4.40%

发文量

511

审稿时长

1.3 months

期刊介绍： With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.