电化学与空间层选核磁共振波谱联用原位监测多碳醇氧化

doi:10.1016/S1872-2067(23)64526-7

催化学报 ›› 2023, Vol. 53: 171-179.DOI: 10.1016/S1872-2067(23)64526-7

• 论文 • 上一篇

电化学与空间层选核磁共振波谱联用原位监测多碳醇氧化

詹昊霖^a^,^b^,¹, 纪丽菲^c^,¹, 曹烁晖^a, 冯烨^a, 姜艳霞^c, 黄玉清^a^,^*(), 孙世刚^c^,^*(), 陈忠^a^,^c^,^*()

^a厦门大学电子科学系, 福建省等离子体与磁共振重点实验室, 福建厦门361005
^b合肥工业大学生物医学工程系, 测量理论与精密仪器安徽省重点实验室, 安徽合肥230009
^c厦门大学化学系, 固体表面物理化学国家重点实验室, 福建厦门361005

收稿日期:2023-07-24 接受日期:2023-10-03 出版日期:2023-10-18 发布日期:2023-10-25
通讯作者: *电子信箱: yqhuangw@xmu.edu.cn (黄玉清), sgsun@xmu.edu.cn (孙世刚), chenz@xmu.edu.cn (陈忠).
作者简介:
¹共同第一作者.
基金资助:
国家自然科学基金(22161142024);国家自然科学基金(22204038);国家自然科学基金(12275228);国家自然科学基金(22073078);国家自然科学基金(21974117);国家重点研发计划(2021YFA1501504);福建省自然科学基金(2021J01053)

In situ monitoring multi-carbon alcohol oxidation by combined electrochemistry with spatially selective NMR spectroscopy

Haolin Zhan^a^,^b^,¹, Lifei Ji^c^,¹, Shuohui Cao^a, Ye Feng^a, Yanxia Jiang^c, Yuqing Huang^a^,^*(), Shigang Sun^c^,^*(), Zhong Chen^a^,^c^,^*()

^aDepartment of Electronic Science, Fujian Provincial Key Laboratory of Plasma and Magnetic Resonance, Xiamen University, Xiamen 361005, Fujian, China
^bDepartment of Biomedical Engineering, Anhui Province Key Laboratory of Measuring Theory and Precision Instrument, Hefei University of Technology, Hefei 230009, Anhui, China
^cDepartment of Chemistry, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, Fujian, China

Received:2023-07-24 Accepted:2023-10-03 Online:2023-10-18 Published:2023-10-25
Contact: *E-mail: yqhuangw@xmu.edu.cn (Y. Huang), sgsun@xmu.edu.cn (S. Sun), chenz@xmu.edu.cn (Z. Chen).
About author:
¹Contributed equally to this work.
Supported by:
The National Natural Science Foundation of China(22161142024);The National Natural Science Foundation of China(22204038);The National Natural Science Foundation of China(12275228);The National Natural Science Foundation of China(22073078);The National Natural Science Foundation of China(21974117);The National Key Research and Development Program of China(2021YFA1501504);The Natural Science Foundation of Fujian Province(2021J01053)

摘要/Abstract

摘要：

醇类燃料电池具有环境友好、运输便利、反应温度低等优势, 被认为是理想的能源替代品之一. 含有两个碳原子以上的多碳醇, 如正丁醇, 在燃料电池应用中具有更高的能量密度和更低的质子膜穿透率等优点. 然而, 多碳醇的氧化反应通常涉及多种C‒C化学键断裂, 产生多种具有相似分子结构的产物和中间产物, 从而增加了产物分析和反应机理研究的难度. 原位电化学核磁共振联用(EC-NMR)技术将核磁共振波谱技术引入到原位电化学实验中, 实时检测电化学反应过程中的谱学信息, 对于深入理解液体燃料电池阳极反应的催化机理有重要应用. 然而, 原位电化学反应过程中磁场的时空变化通常会导致核磁共振谱峰展宽和谱图分辨率不足的问题, 使其应用受到限制.

本文将传统电化学方法与空间层选核磁共振波谱技术进行联用(EC-SPSENMR)以应对该挑战, 实现多碳有机分子电催化过程的原位实时分析. 该策略可以很好地克服原位电化学反应过程中磁场时空变化引起谱图分辨率不足等问题, 在原位测量时能够记录具有清晰J偶合裂分结构的高分辨谱峰, 实现对电化学反应进程中不同分子信息的直接识别, 便于后续的定性和定量分析. 此外, 该策略还可直接在标准的商业核磁共振波谱仪器上使用, 从中提取分辨率高且谱峰形状未失真的核磁共振信号用于电化学分析, 且对电极材料和电极放置位置几乎没有特殊要求, 因此可广泛适用于原位电化学研究. 本文以正丁醇电氧化为例, 探究了该技术应用于多碳醇氧化的原位监测以及相关机理研究的可行性和有效性. 结果表明, 相较于原位红外实验, EC-SPSENMR实验可直接观测和区分氧化产物中的正丁酸和乙酸. 特别是当工作温度为60 °C时, 商业催化剂Pt/C在高电位下直接氧化正丁醇生成正丁酸的反应更显著, 而随着电位降低, 正丁醇氧化生成气态产物(主要是CO₂)的比例升高. 此外, 在1.2 V电位(相对于SCE)下, 相较于催化剂PtRu/C, 采用商业催化剂Pt/C时正丁醇氧化生成气态产物的比例更高. 说明在1.2 V的高电位下, 相比于PtRu/C, Pt/C可能更倾向于辅助β-C-H键断裂过程.

综上所述, 相比于传统的EC-NMR实验, 本文提出的EC-SPSENMR方案可以有效克服原位电化学反应过程中磁场变化引起的谱图分辨率低的问题, 为实时监测电化学过程、研究氧化机理和评估催化特性提供了有效手段. 此外, 为液体燃料电池研究, 尤其是多碳醇燃料电池的阳极电氧化反应研究, 提供了一个有应用前景的范例, 对进一步扩展核磁共振在电化学的应用提供参考.

关键词: 电化学核磁共振联用, 空间层选, 原位检测, 正丁醇电氧化, 液体燃料电池

Abstract:

In situ electrochemical nuclear magnetic resonance (EC-NMR) plays a pivotal role in electrochemical observation on liquid fuel cells, but its applications are generally trapped by insufficient spectral resolution caused by spatiotemporal variations of magnetic fields. Herein, we develop a general spectroelectrochemistry protocol to address this problem and facilitate real-time electrooxidation analyses. This protocol enables the direct extraction of well-resolved and undistorted NMR signals from standard NMR instruments, thus it is commonly applicable to in situ electrochemical studies. The effectiveness for electrooxidation mechanism investigations on multi-carbon alcohols is validated by 1-butanol electrooxidation. It is verified that the direct oxidation of 1-butanol to butyric acid becomes more significant along with higher potentials on Pt/C at 60 °C, while 1-butanol oxidation is more likely to yield gaseous products (mainly CO₂) at lower potentials. Additionally, this protocol reveals that Pt/C rather than PtRu/C is inclined to accomplish the β-C-H bond breaking process for CO₂ generation at a high potential of 1.2 V (vs. SCE). Therefore, this study provides a promising paradigm for electrooxidation investigations on fuel cells, and it may take a meaningful step toward wider electrochemical studies and NMR applications.

Key words: Electrochemical nuclear magnetic resonance, Spatially selective, In situ investigation, 1-Butanol electrooxidation, Liquid fuel cell

詹昊霖, 纪丽菲, 曹烁晖, 冯烨, 姜艳霞, 黄玉清, 孙世刚, 陈忠. 电化学与空间层选核磁共振波谱联用原位监测多碳醇氧化[J]. 催化学报, 2023, 53: 171-179.

Haolin Zhan, Lifei Ji, Shuohui Cao, Ye Feng, Yanxia Jiang, Yuqing Huang, Shigang Sun, Zhong Chen. In situ monitoring multi-carbon alcohol oxidation by combined electrochemistry with spatially selective NMR spectroscopy[J]. Chinese Journal of Catalysis, 2023, 53: 171-179.

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图/表 3

Fig. 1. In situ electrooxidation observation of a blend alcohol sample (containing 0.2 mol L-1 1-butanol, 0.1 mol L-1 ethanol, and 0.1 mol L-1 2-propanol in 0.1 mol L-1 HClO4) on Pt/C at 1.2 V (vs. SCE). (a) Pulse sequences of standard 1D single-pulse NMR, 1D spatially selective NMR methods (SPSE-I and SPSE-II). (b) Schematic in situ electrochemical setups. (c,d) Time-resolved 1D spectra acquired by the 1D single-pulse NMR and SPSE-II sequences. (e) Expanded spectral regions between 0.80 and 1.70 ppm in (d). (f) Predicted electrooxidation mechanism and possible oxidation pathways. The blue region in Fig. 1(d) is expanded to exhibit the fine spectra between 1.90 and 2.50 ppm. The experimental details are given in Supporting Information.

Fig. 2. Experimental results on 0.2 mol L?1 1-butanol and 0.1 mol L?1 HClO4 solution at 60 °C. Quantification results at 1.0 V (a), 0.75 V (b), and 0.5 V (c) on Pt/C, in which the amount of gaseous products (mainly CO2) is calculated by the difference between reactants and products based on the mass conservation law. Normalized conversion rates (d) and product selectivities (e) at three potentials measured form the last in situ SPSE spectra. (f) Possible reaction mechanism of 1-butanol oxidation on Pt/C.

Fig. 3. Experimental results on 1-butanol electrooxidation on two catalysts. Quantitative intensities of 1-butanol, butyric acid, acetic acid, and CO2 during 1-butanol oxidation on Pt/C (a) and PtRu/C (b), respectively. In situ EC-SPSENMR experiments are performed at 1.2 V at 60 °C. (c) Normalized contents of individual molecules were calculated based on the last in situ SPSE spectra. (d) The product selectivities on two electrocatalysts. (e) The predicted schematic diagrams of the 1-butanol oxidation on Pt/C and PtRu/C at 1.2 V.

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电化学与空间层选核磁共振波谱联用原位监测多碳醇氧化

In situ monitoring multi-carbon alcohol oxidation by combined electrochemistry with spatially selective NMR spectroscopy

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