局域静电环境工程用于增强电催化生物质转化过程中羟基活性

doi:10.1016/S1872-2067(23)64516-4

催化学报 ›› 2023, Vol. 53: 153-160.DOI: 10.1016/S1872-2067(23)64516-4

局域静电环境工程用于增强电催化生物质转化过程中羟基活性

逯宇轩^a^,¹, 杨柳^b^,¹, 姜一民^b, 原甑然^b^,^c, 王双印^b, 邹雨芹^b^,^*()

^a山西大学化学化工学院, 山西太原030006
^b湖南大学化学化工学院, 教育部高级催化工程研究中心, 化学/生物传感与化学计量学国家重点实验室, 湖南长沙410082
^c湖南大学深圳研究院, 广东深圳518057

收稿日期:2023-07-11 接受日期:2023-08-25 出版日期:2023-10-18 发布日期:2023-10-25
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:
国家重点研发计划(2020YFA0710000);国家自然科学基金(22122901);湖南省自然科学基金(2021JJ0008);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)

Engineering a localized electrostatic environment to enhance hydroxyl activating for electrocatalytic biomass conversion

Yuxuan Lu^a^,¹, Liu Yang^b^,¹, Yimin Jiang^b, Zhenran Yuan^b^,^c, Shuangyin Wang^b, Yuqin Zou^b^,^*()

^aSchool of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, Shanxi, China
^bState Key Laboratory of Chemo/Bio-Sensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, Hunan, China
^cShenzhen Institute of Hunan University, Shenzhen 518057, Guangdong, China

Received:2023-07-11 Accepted:2023-08-25 Online:2023-10-18 Published:2023-10-25
Contact: *E-mail: yuqin_zou@hnu.edu.cn (Y. Zou).
About author:
¹ Contributed equally to this work.
Supported by:
The National Key R&D Program of China(2020YFA0710000);The National Natural Science Foundation of China(22122901);The Provincial Natural Science Foundation of Hunan(2021JJ0008);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：

作为一种可再生碳源, 5-羟甲基糠醛(HMF)是一种重要的生物质平台分子, 已被广泛用于制造医药前体、单体和精细化学品. HMF的电催化氧化反应(HMFOR)是一种在常温常压下实现HMF向2,5-呋喃二甲酸(FDCA)转化的高效绿色过程. 但与传统的析氧反应(OER)不同, HMFOR相对复杂, 需要经过6个电子的转移过程, 分别涉及羟基和醛基的氧化. 研究发现, NiO对羟基氧化具有较高的反应活性, 但HMFOR反应途径受溶液pH值的影响, 醛基以二元醇的形式优先在碱性溶液中被吸附和活化, 从而导致反应活性较低.

本文引入了导电聚合物聚吡咯(PPy), 通过X射线光电子能谱(XPS)、原位红外光谱(FTIR)、高效液相色谱(HPLC)、密度泛函理论计算(DFT)、原位电化学石英晶体微天平(EQCM)等表征技术研究了PPy在引入NiO后对HMFOR的影响和催化性能差异的原因. X射线衍射结果表明, PPy引入的聚合过程没有破坏NiO的晶体结构, 而FTIR显示出PPy分子中吡咯环的C‒H弯曲振动及芳香胺分子中N‒H的伸缩振动, 说明PPy成功引入NiO表面. 高分辨透射电镜结果表明, PPy以5 nm平均厚度薄层覆盖在NiO表面. 此外, XPS结果证实了Ni, O, C和N元素的存在, 吡咯氮(‒NH‒)物种在NiO-PPy电催化剂中占主导地位, 而Ni 2p_3/2和O 1s的XPS谱中NiO和NiO-PPy且有相似的电子结构, 说明PPy的引入并没有改变NiO的电子结构. 线性扫描伏安曲线和电化学活性面积测试结果表明, PPy的引入显著提高了HMFOR的电流密度和NiO的内在活性. 同时, NiO-PPy比NiO具有更低的Tafel斜率, 表明PPy会提高HMFOR的反应动力学, 加速HMF转化. 电解测试中高效液相色谱分析结果表明, 在前0.5 h内NiO-PPy催化剂上HMF转化率高于NiO催化剂, 说明PPy的引入加速了HMF的转化. 此外, 分析中间产物发现, NiO催化剂上的HMFOR中间体主要为5-羟甲基呋喃-2-羧酸, 而NiO-PPy上主要为2,5-二甲酰基呋喃. 周期性测试结果表明, NiO-PPy表现出较高的HMF转化率和产物选择性, 且具有较好的稳定性. 运用开路电位和电化学石英晶体微天平检测了HMF分子在NiO和NiO-PPy上的吸附能力. 结果表明, PPy涂层明显增强了HMF分子在NiO上的吸附能力. 采用表面增强红外吸收光谱研究了电催化剂表面重要中间体的吸附行为. 结果表明, NiO上HMFOR路径主要为HMFCA路径, 而在NiO-PPy上新增2,5-二甲酰基呋喃, 表明HMF分子的羟基和醛基同时在NiO-PPy表面被激活, 进一步说明PPy的引入会选择性地提升羟基氧化的反应性能, 进而提升了HMFOR活性. 采用密度泛函理论研究了PPy的作用, 结果表明正电性PPy分子会吸引电负性的羟基, 缩短Ni与醛基之间的键长, 降低醛基的反应活性, 调节HMFOR反应途径, 进而获得更高的HMFOR性能.

综上所述, 本文通过导电聚合物PPy修饰调控了电极界面微环境以及表面电性, 从而调控了HMF分子的吸附构型和反应路径, 获得更高的HMF电催化氧化反应活性. 本文为HMF氧化高效电催化剂的设计提供了新的思路, 并为HMF电催化氧化应用化研究提供借鉴.

关键词: 电催化剂, 表面微环境, 生物质改性, 聚合物改性, 电催化氧化

Abstract:

The 5-hydroxymethylfurfural electrocatalytic oxidation reaction (HMFOR) is a sustainable and efficient route for converting biomass platform molecules into high-value chemicals. The HMFOR process involves the simultaneous oxidation of hydroxyl and aldehyde groups. Optimizing the reaction pathways by modulating the adsorption behavior of 5-Hydroxymethylfurfural molecules toward a higher conversion rate is vital for achieving an efficient HMFOR. In this study, the HMFOR electrocatalytic performance of NiO was enhanced by regulating the surface microenvironment through the decoration of NiO nanosheets with polypyrrole (PPy). Operando Fourier transform infrared spectroscopy, density functional theory calculation, and electrochemical behavior characterizations demonstrated that electropositive PPy can optimize the adsorption behavior of electronegative hydroxyl groups and modulate the reaction pathway toward the formation of 2,5-diformylfuran intermediates. By modulating the local microenvironment, the designed NiO-PPy catalyst showed excellent HMFOR performance with a threefold increase in current density. This study emphasizes the significance of the surface microenvironment in modulating reaction pathways to achieve selective biomass electrocatalytic conversion.

Key words: Electrocatalyst, Surface micro-environment, Biomass upgrading, Polymer modification, Electrocatalytic oxidation

逯宇轩, 杨柳, 姜一民, 原甑然, 王双印, 邹雨芹. 局域静电环境工程用于增强电催化生物质转化过程中羟基活性[J]. 催化学报, 2023, 53: 153-160.

Yuxuan Lu, Liu Yang, Yimin Jiang, Zhenran Yuan, Shuangyin Wang, Yuqin Zou. Engineering a localized electrostatic environment to enhance hydroxyl activating for electrocatalytic biomass conversion[J]. Chinese Journal of Catalysis, 2023, 53: 153-160.

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Fig. 1. (a) XRD patterns of NiO and NiO-PPy. (b) FT-IR spectra of NiO and NiO-PPy. HR-TEM images of NiO (c) and NiO-PPy (d). (e) XPS survey spectra of NiO-PPy. (f) N 1s in the NiO-PPy.

Fig. 2. (a) LSV curves of HMFOR on PPy, NiO, and NiO-PPy at a scan rate of 5 mV s?1. (b) Tafel slope of NiO and NiO-PPy. (c) Relative content of HMF during the electrolysis on NiO and NiO-PPy at the potential of 1.45 VRHE. (d) HMF conversion and FDCA yield of NiO-PPy under six successive electrolysis cycles at the potential of 1.45 VRHE and the electrolysis time of 1.5 h. (e) FT-IR spectra of NiO-PPy before and after electrolysis. (f) XPS spectra of N 1s in NiO-PPy before and after electrolysis.

Fig. 3. (a) OCP measurement of NiO and NiO-PPy. (b) EQCM curves of NiO and NiO-PPy. (c) Detailed HMF oxidation reaction pathways. (d) Concentration of HMFCA and DFF on NiO and NiO-PPy during HMFOR. (e) Concentration of intermediates on NiO-PPy during HMFOR. Operando FT-IR spectra of NiO (f) and NiO-PPy (g).

Fig. 4. (a) LSV curves of NiO and NiO-PPy in 1 mol L?1 KOH or with 50 mmol L?1 organic molecule. (b) Comparison of HMFOR, FAOR, and FFOR performance between NiO-PPy and NiO at the potential of 1.45 VRHE. (c) Adsorption model of HMF molecule on NiO and NiO-PPy. (d) Comparison of the adsorption energy of HMF molecule on NiO and NiO-PPy. (e) Scheme for the modulation of the surface micro-environment by decorating PPy on NiO to achieve HMFOR process.

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局域静电环境工程用于增强电催化生物质转化过程中羟基活性

Engineering a localized electrostatic environment to enhance hydroxyl activating for electrocatalytic biomass conversion

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