通过TEMPO增强脱氢和OH吸附促进中性电解质中5-羟甲基糠醛的电催化氧化

doi:10.1016/S1872-2067(22)64203-7

催化学报 ›› 2023, Vol. 46: 148-156.DOI: 10.1016/S1872-2067(22)64203-7

通过TEMPO增强脱氢和OH吸附促进中性电解质中5-羟甲基糠醛的电催化氧化

王洪芳^a, 徐雷涛^a, 吴景程^a, 周鹏^a, 陶沙沙^a, 逯宇轩^a, 吴贤文^b, 王双印^a, 邹雨芹^a^,^*()

^a湖南大学化学化工学院, 先进催化教育部工程研究中心, 化学生物传感与计量学国家重点实验室, 湖南长沙 410082
^b吉首大学化学化工学院, 湖南吉首 416000

收稿日期:2022-10-04 接受日期:2022-11-29 出版日期:2023-03-18 发布日期:2023-02-21
通讯作者: *电子信箱: yuqin_zou@hnu.edu.cn (邹雨芹)
作者简介:
¹共同第一作者
基金资助:
国家重点研发项目(2020YFA0710000);国家自然科学基金(22122901);国家自然科学基金(21902047);湖南省自然科学基金(2020JJ5045);湖南省自然科学基金(2021JJ20024);湖南省自然科学基金(2021RC3054);深圳市科学技术计划(JCYJ20210324140610028)

Boosting 5-hydroxymethylfurfural electrooxidation in neutral electrolytes via TEMPO-enhanced dehydrogenation and OH adsorption

Hongfang Wang^a, Leitao Xu^a, Jingcheng Wu^a, Peng Zhou^a, Shasha Tao^a, Yuxuan Lu^a, Xianwen Wu^b, Shuangyin Wang^a, Yuqin Zou^a^,^*()

^aState Key Laboratory of Chem/Bio-Sensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, the National Supercomputer Centers in Changsha, Hunan University, Changsha 410082, Hunan, China
^bSchool of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, Hunan, China

Received:2022-10-04 Accepted:2022-11-29 Online:2023-03-18 Published:2023-02-21
Contact: *E-mail: yuqin_zou@hnu.edu.cn (Y. Zou)
About author:
¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2020YFA0710000);The National Natural Science Foundation of China(22122901);The National Natural Science Foundation of China(21902047);The Provincial Natural Science Foundation of Hunan(2020JJ5045);The Provincial Natural Science Foundation of Hunan(2021JJ20024);The Provincial Natural Science Foundation of Hunan(2021RC3054);The Shenzhen Science and Technology Program(JCYJ20210324140610028)

摘要/Abstract

摘要：

生物质衍生物的电催化转化为可持续能源的增值利用提供了一条绿色高效的途径. 例如, 由5-羟甲基糠醛(HMF)氧化可得到生物基聚酯前驱体2,5-呋喃二甲酸(FDCA), 对于缓解化石资源带来的能源危机和环境问题具有重要意义. 目前, HMF的电催化氧化通常在强碱性(pH>13.5)溶液中进行, 但是容易产生难以分离的腐殖质, 影响FDCA的工业利用. 另外, 强碱性介质还存在腐蚀安全隐患、设备维护成本高等问题. 中性反应条件有助于改善上述问题, 但是缺乏亲电氧物种(例如OH^‒), HMF和催化剂的活化困难, 难以得到高附加值产物FDCA. 目前, 针对中性介质中HMF的电催化氧化研究少有报道, 急需明晰中性介质中HMF的催化机理, 并开发中性条件下具有高活性的催化剂体系.

本文利用均相催化剂2,2,6,6-四甲基哌啶-1-氧基(TEMPO)和Co₃O₄电极, 对HMF进行中性条件下电催化氧化, 1.55 V_RHE条件下反应1.5 h, 以接近100%转化率获得产物FDCA, 产率大于99%. 而在无TEMPO的条件下, HMF在Co₃O₄电极上转化率小于2%. 原位红外等实验测试及理论计算结果表明, 低电位(1.10 V_RHE)下形成的TEMPO⁺阳离子的活化能显著减低HMF, 通过脱氢作用选择性生成中间产物2,5-二甲酰基呋喃(DFF), 对调控HMF的氧化路径、促进中性介质电催化氧化起到关键作用.

原位X射线光电子能谱和电化学阻抗等结果发现, TEMPO存在时, 1.35 V后, 在含有高价态Co^3+/4+的Co₃O₄电极上出现更多的水以及OH吸附物种, 并导致HMF的氧化电流密度以及FDCA的转化率显著增加. 理论计算结果表明, TEMPO自由基与水分子存在较强的氢键作用, 有利于促进水活化提供OH. 然而, 低电位(1.25 V)以Co₃O₄为电极, 或高电位(1.55 V)以泡沫镍为电极, 即使添加TEMPO, 电极上没有出现相应的OH吸附行为和电化学活性提升现象. 因此, 活性的Co₃O₄电极对于协同水的解离形成OH具有重要作用, 二者共同作用下, 水活化解离形成Co^3+/4+-(OH)_ads活性中心. 在中性溶液中, 亲电氧物种OH_ads提供氧源, 促进DFF等甲酰基中间体进一步氧化转化为FDCA. 综上, 本文加深了对中性介质中HMF的电催化氧化机制的理解, 对设计类似电催化剂体系有借鉴作用.

关键词: 5-羟甲基糠醛, 电催化氧化, 2,2,6,6-四甲基哌啶-1-氧基, 中性电解, 中性电解质, 生物质电催化

Abstract:

5-Hydroxymethylfurfural (HMF) electrooxidation in neutral conditions is a promising strategy to suppress the formation of humins and corrosive effects on electrochemical devices. However, scarce studies have been reported in neutral media due to the deficiency in electrophilic oxygen (eg OH^‒) required for the activation of HMF. Herein, 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO)/Co₃O₄ was utilized to co-catalyze HMF in neutral media, successfully achieving 2,5-furandicarboxylic acid (FDCA) with yield > 99%. It was found that TEMPO could promote HMF dehydrogenation to 2,5-diformylfuran (DFF) and simultaneously activated water via hydrogen-bonding interactions. As a result, the formation of OH^* in neutral electrolytes was favored, which was absorbed by electrogenerated active Co species to facilitate subsequent conversion of formyl-group-involved intermediates to FDCA. This work provides a current understanding of the catalytic mechanism for HMFOR in neutral media and guides the design of highly efficient electrocatalysts for biomass upgrading.

Key words: 5-Hydroxymethylfurfural, Electrooxidation, 2,2,6,6-tetramethyl-piperidine-1-oxyl, Neutral electrolyte, Biomass electrocatalysis

王洪芳, 徐雷涛, 吴景程, 周鹏, 陶沙沙, 逯宇轩, 吴贤文, 王双印, 邹雨芹. 通过TEMPO增强脱氢和OH吸附促进中性电解质中5-羟甲基糠醛的电催化氧化[J]. 催化学报, 2023, 46: 148-156.

Hongfang Wang, Leitao Xu, Jingcheng Wu, Peng Zhou, Shasha Tao, Yuxuan Lu, Xianwen Wu, Shuangyin Wang, Yuqin Zou. Boosting 5-hydroxymethylfurfural electrooxidation in neutral electrolytes via TEMPO-enhanced dehydrogenation and OH adsorption[J]. Chinese Journal of Catalysis, 2023, 46: 148-156.

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图/表 5

Fig. 1. (a) XRD pattern of bare NF and Co3O4/NF. SEM (b) and TEM (c) images of Co3O4. (d) LSV curves of Co3O4 in PBS electrolytes with different substrates. (e) Conversion of HMF, yield, and Faradaic efficiency (FE) of FDCA for 10 mmol L-1 HMF oxidation on Co3O4 at 1.55 VRHE for 1.5 h in the absence and presence of 20 mmol L-1 TEMPO. (f) Yield and FE of FDCA in relationship with the electrolysis potential.

Fig. 2. (a,b) Product quantitative analysis by HPLC during HMF electrolysis on Co3O4 at 1.55 VRHE in the absence (duration 47 h) and presence of TEMPO (duration 1.5 h). (c) Two possible pathways of HMF oxidation to FDCA. (d,e) Operando ATR-SEIRAS spectra traced for Co3O4-catalyzed HMF oxidation in the absence and presence of TEMPO.

Fig. 3. HMF oxidation reaction profiles by hydration reaction mechanism (black color) and TEMPO-mediated mechanism (orange color). RC is the reaction complex of TEMPO+ and HMF. 1 is the hydrated HMF. The TS and TS-1 represent the transition state for HMF oxidation via TEMPO and hydration reaction, respectively. Int-1 and DFF-H+ are HMF intermediates formed correspondingly by two routes.

Fig. 4. Operando Bode phase plots of Co3O4 at various applied potentials in blank neutral PBS electrolytes (a) and the counterparts with 10 mmol L?1 HMF (b), 10 mmol L?1 TEMPO (c), and the coexistence of 10 mmol L?1 HMF and TEMPO (d). Preferential H-bond distance and structure change of H2O molecule under the effect of TEMPO radical (e) and TEMPO+ cation (f).

Fig. 5. (a) Co 2p3/2 XPS spectrum fitting for Co3O4 pre-treated after catalyzing HMF oxidation at corresponding potentials. (b) Current density for HMF electrolysis on different electrodes at different potentials (E = 1.05-1.65 VRHE) in 1 mol L?1 PBS neutral solutions (HMF 10 mmol L?1, TEMPO 20 mmol L?1). (c) A scheme depicts the possible reaction process for HMF electrooxidation on the Co3O4 electrode in neutral electrolytes under the effects of TEMPO.

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通过TEMPO增强脱氢和OH吸附促进中性电解质中5-羟甲基糠醛的电催化氧化

Boosting 5-hydroxymethylfurfural electrooxidation in neutral electrolytes via TEMPO-enhanced dehydrogenation and OH adsorption

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