碳纳米管负载钯基催化剂催化氧化2,5-呋喃二甲醇合成2,5-呋喃二甲酸

doi:10.1016/S1872-2067(21)63878-0

催化学报 ›› 2022, Vol. 43 ›› Issue (3): 793-801.DOI: 10.1016/S1872-2067(21)63878-0

碳纳米管负载钯基催化剂催化氧化2,5-呋喃二甲醇合成2,5-呋喃二甲酸

李振宇^a^,^†, 淮丽媛^a^,^†, 郝盼盼^a^,^*(), 赵玺^a, 王永钊^b, 张炳森^b, 谌春林^a, 张建^a^,^#()

^a中国科学院宁波材料技术与工程研究所, 浙江宁波 315201
^b中国科学院金属研究所, 沈阳材料科学国家研究中心, 辽宁沈阳 110016

收稿日期:2021-04-07 修回日期:2021-04-07 出版日期:2022-03-18 发布日期:2022-02-18
通讯作者: 郝盼盼,张建
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家自然科学基金(22072170);中国科学院前沿科学重点研究项目(QYZDB-SSW-JSC037);宁波市重大专项(2018B10056);宁波市重大专项(2019B10096)

Oxidation of 2,5-bis(hydroxymethyl)furan to 2,5-furandicarboxylic acid catalyzed by carbon nanotube-supported Pd catalysts

Zhenyu Li^a^,^†, Liyuan Huai^a^,^†, Panpan Hao^a^,^*(), Xi Zhao^a, Yongzhao Wang^b, Bingsen Zhang^b, Chunlin Chen^a, Jian Zhang^a^,^#()

^aNingbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China
^bShenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, Liaoning, China

Received:2021-04-07 Revised:2021-04-07 Online:2022-03-18 Published:2022-02-18
Contact: Panpan Hao, Jian Zhang
About author:First author contact:
^† These authors contributed equally.
Supported by:
National Natural Science Foundation of China(22072170);Chinese Academy of Sciences(QYZDB-SSW-JSC037);Ningbo Science and Technology Bureau(2018B10056);Ningbo Science and Technology Bureau(2019B10096)

摘要/Abstract

摘要：

为积极应对化石能源枯竭和生态环境日益严峻等问题, 可再生生物质资源的深度开发并进一步替代传统能源或石化原料被广泛认可. 利用高效催化技术将生物质资源转化为高附加值的平台化合物, 有望衍生出大量具备新颖结构与功能的绿色化学品. 2,5-呋喃二甲酸(FDCA)作为重要的生物质基平台化合物之一, 具有巨大的市场应用价值, 其中因其与化石基对苯二甲酸(PTA)有着极其相似的化学结构, 以FDCA替代PTA作为合成单体制备大宗聚合物备受关注. 以5-羟甲基糠醛(HMF)为原料, 采用多相催化体系(主要是贵金属催化剂)选择氧化制备FDCA是目前广泛采用的方法. 但“HMF路线”面临一些基础性的难题, 如HMF熔点较低, 需低温存储, 增加了实际应用中的运输成本; HMF在碱性溶液中易降解, 导致反应过程中碳平衡损失; HMF结构中含有的不对称的羟基和醛基官能团在氧化反应中会发生竞争反应, 致使反应副产物较多; 此外, 碱性反应介质中通常会得到醛基优先氧化的中间体5-羟甲基-2-呋喃甲酸(HMFCA), 但由于HMFCA结构中羧基官能团的存在使得羟基进一步氧化较为困难, 通常需要增加碱浓度、提升温度或压力, 使反应条件变得苛刻. 因此, 寻求新的原料替代HMF, 实现温和条件下高效合成FDCA具有重要意义.
本文采用改性后的碳纳米管负载Pd催化剂(Pd/o-CNT), 从具有独特对称结构的2,5-二羟甲基呋喃(BHMF)出发, 提出一种新颖、高效催化合成FDCA的“BHMF路线”. 反应在60 °C常压下进行, BHMF在20 min内即可完全转化, 60 min后FDCA的产率最高可达93.0%, 优于相同条件下HMF为原料时的性能(FDCA产率仅为35.7%). 相比于未作处理的碳纳米管负载钯催化剂(Pd/CNT), Pd/o-CNT催化剂具有更高含量的氢化钯(PdH_x)物种, 显著促进了FDCA产率的提升. Pd/o-CNT在循环使用10次后, BHMF仍能完全转化, FDCA产率维持在75%. 稳定性下降可能与活性物种流失、团聚及价态变化有关. 基于对照试验, 本文提出了可能的反应路径, 即BHMF主要是通过2,5-二甲酰基呋喃和5-甲酰基-2-呋喃甲酸作为过程中间体, 有效转化为FDCA, 从而规避并减少生成HMF和活性较低的HMFCA. 本文通过以新原料BHMF作底物, 实现了高效制备生物基平台化合物FDCA, 为生物质的产业化应用提供了新的研究思路.

关键词: 2,5-呋喃二甲醇, 2,5-呋喃二甲酸, 氢化钯, 5-羟甲基糠醛, 催化氧化

Abstract:

The selective oxidation of 2,5-bis(hydroxymethyl)furan (BHMF) in this work was proven as a promising route to produce 2,5-furandicarboxylic acid (FDCA), an emerging bio-based building-block with wide application. Under ambient pressure, the modified carbon nanotube-supported Pd-based catalysts demonstrate the maximum FDCA yield of 93.0% with a full conversion of BHMF after 60 min at 60 °C, much superior to that of the traditional route using 5-hydroxymethylfurfural (HMF) as substrates (only a yield of 35.7%). The participation of PdH_x active species with metallic Pd can be responsible for the encouraging performance. Meanwhile, a possible reaction pathway proceeding through 2,5-diformylfuran (DFF) and 5-formyl-2-furancarboxylic acid (FFCA) as process intermediates is suggested for BHMF route. The present work may provide new opportunities to synthesize other high value-added oxygenates by using BHMF as an alternative feedstock.

Key words: 2,5-Bis(hydroxymethyl)furan, 2,5-Furandicarboxylic acid, Palladium hydride, 5-Hydroxymethylfurfural, Catalytic oxidation

李振宇, 淮丽媛, 郝盼盼, 赵玺, 王永钊, 张炳森, 谌春林, 张建. 碳纳米管负载钯基催化剂催化氧化2,5-呋喃二甲醇合成2,5-呋喃二甲酸[J]. 催化学报, 2022, 43(3): 793-801.

Zhenyu Li, Liyuan Huai, Panpan Hao, Xi Zhao, Yongzhao Wang, Bingsen Zhang, Chunlin Chen, Jian Zhang. Oxidation of 2,5-bis(hydroxymethyl)furan to 2,5-furandicarboxylic acid catalyzed by carbon nanotube-supported Pd catalysts[J]. Chinese Journal of Catalysis, 2022, 43(3): 793-801.

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图/表 8

Fig. 1. The time courses of normalized substrate concentrations. Reaction condition: No catalysts, substrate 20 mM, H2O 30 mL, NaOH/substrate (molar ratio) 10/1, 60 °C, 60 min.

Fig. 2. Effects of the pretreatment of CNTs on catalytic behaviors of the Pd/CNT catalysts for BHMF oxidation. Notably, the Pd/CNT sample with CNTs pretreated by 30 wt% HNO3 is specified as Pd/o-CNT in the main text. Reaction conditions: BHMF 20 mM, BHMF/Pd (molar ratio) 50/1, H2O 30 mL, NaOH/BHMF (molar ratio) 10/1, 60 °C, 100 ml/min O2, 60 min.

Table 1 Physicochemical properties and catalytic performances of carbon nanotube-supported Pd catalysts for BHMF oxidation. a

Entry	Catalyst	Pd loading ^b (wt %)	Mean particle size ^c (nm)	S(PdH_x)/S(Pd⁰) ^d	I_D/I_G ratio ^e	BHMF conv. (%)	Yield (%)
Entry	Catalyst	Pd loading ^b (wt %)	Mean particle size ^c (nm)	S(PdH_x)/S(Pd⁰) ^d	I_D/I_G ratio ^e	BHMF conv. (%)	FDCA	HMFCA	FFCA	HMF
1	Pd/CNT	4.7	4.0	2.0	1.22	>99	71.0	13.2	12.0	0.2
2	Pd/o-CNT	4.8	4.2	4.4	1.22	>99	93.0	4.8	0	0
3	Pd/o-CNT-10runs	4.1	6.7	3.2	—	>99	75.1	24.4	0	0

Fig. 3. TEM images and the corresponding particle size distributions of Pd/CNT (a,b) and Pd/o-CNT (c,d).

Fig. 4. Raman spectra (a), XRD pattern (b), TPDMS profile (c) and XPS Pd 3d spectra (d) for Pd/CNT and Pd/o-CNT.

Fig. 5. (a) Stability of the Pd/o-CNT catalyst during the recycling uses for BHMF oxidation. Reaction conditions: BHMF 20 mM, BHMF/Pd (molar ratio) 50/1, H2O 30 mL, NaOH/BHMF (molar ratio) 10/1, 60 °C, 100 ml/min O2, 60 min. TEM image (b), XRD pattern (c) and XPS Pd 3d spectra (d) for the spent Pd/o-CNT-10runs catalyst.

Fig. 6. The time courses for the oxidation of BHMF (a) and HMF (b) over Pd/o-CNT under a NaOH/substrate molar ratio of 10:1. Effect of the base concentration on catalytic behavior of the Pd/o-CNT catalyst for the oxidation of BHMF (c) and HMF (d). Reaction conditions: substrate 20 mM, substrate/Pd (molar ratio) 50/1, H2O 30 mL, 60 °C, 100 ml/min O2, 60 min.

Fig. 7. (a) The proposed reaction pathway for BHMF oxidation over the Pd/o-CNT catalyst. The time courses for the oxidation of DFF (b) and FFCA (c) over Pd/o-CNT. Reaction conditions: substrate 20 mM, substrate/Pd (molar ratio) 50/1, H2O 30 mL, 60 °C, 100 ml/min O2, 60 min.

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碳纳米管负载钯基催化剂催化氧化2,5-呋喃二甲醇合成2,5-呋喃二甲酸

Oxidation of 2,5-bis(hydroxymethyl)furan to 2,5-furandicarboxylic acid catalyzed by carbon nanotube-supported Pd catalysts

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