pH诱导的铜电极上糠醛选择性电催化氢化

doi:10.1016/S1872-2067(22)64119-6

催化学报 ›› 2022, Vol. 43 ›› Issue (12): 3142-3153.DOI: 10.1016/S1872-2067(22)64119-6

pH诱导的铜电极上糠醛选择性电催化氢化

周灵^a^,^†, 李莹莹^a^,^†, 逯宇轩^a, 王双印^a, 邹雨芹^a^,^b^,^*()

^a湖南大学化学化工学院, 教育部高等催化工程研究中心, 化学生物传感与计量学国家重点实验室, 湖南长沙410082
^b湖南大学深圳研究所, 广东深圳518057

收稿日期:2022-03-23 接受日期:2022-04-25 出版日期:2022-12-18 发布日期:2022-10-18
通讯作者: 邹雨芹
作者简介:第一联系人：
^†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)

pH-Induced selective electrocatalytic hydrogenation of furfural on Cu electrodes

Ling Zhou^a^,^†, Yingying Li^a^,^†, Yuxuan Lu^a, Shuangyin Wang^a, Yuqin Zou^a^,^b^,^*()

^aState 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
^bShenzhen Institute of Hunan University, Shenzhen 518057, Guangdong, China

Received:2022-03-23 Accepted:2022-04-25 Online:2022-12-18 Published:2022-10-18
Contact: Yuqin Zou
About author:First author contact:^†Contributed equally to this work.
Supported by:
National Key R&D Program of China(2020YFA0710000);National Natural Science Foundation of China(22122901);National Natural Science Foundation of China(21902047);Provincial Natural Science Foundation of Hunan(2020JJ5045);Provincial Natural Science Foundation of Hunan(2021JJ20024);Provincial Natural Science Foundation of Hunan(2021RC3054);Shenzhen Science and Technology Program(JCYJ20210324140610028)

摘要/Abstract

摘要：

以石油化工为支柱的能源体系排放过量的碳, 致使人类面临日益增大的生态压力. 因此, 迫切需要发展以可再生能源为核心的新一代能源体系. 作为新兴能源技术之一, 生物质平台化合物的电催化氢化反应(ECH)可以在常温常压下进行生物燃油精炼和高价值化学品生产, 不需要外部氢气供应, 并且易于形成分布式能源系统. 结合清洁电力可以促进能源转换并实现碳中和. 然而, ECH的机理研究尚处于初步阶段, 提高ECH效率和选择性调控机制仍然是未来的研究重点. 铜电极上糠醛的ECH反应受到电解液pH的显著影响: 在强酸中糠醛选择性发生氢解反应生成2-甲基呋喃(MF), 而在中碱性条件下高选择性加氢生成糠醇(FA). 目前糠醛ECH主流的反应机理是氢转移机制, 即Volmer反应生成的吸附氢(H_ad)与吸附在电极表面的糠醛直接发生氢化反应, 动力学上符合LH (Langmuir-Hinshelwood)机理. 然而, 其他文献未能提出合理的pH影响原因, 仅套用可能的动力学模型对实验数据进行拟合, 或从传质效应来推测MF的生成与电极表面高H_ad覆盖度有关. 然而这些研究没有进行电极表面物种的分析, 尤其是不同pH值下Cu表面吸附中间体的表征, 因此, 有必要通过逐步分析、跟踪观察, 设计准确、系统的控制实验, 并梳理反应的关键步骤来确定电解环境对ECH性能和选择性的调控机制.

本文对Cu催化的糠醛ECH反应中pH的影响进行了全面的电动力学研究. 研究结果表明, ECH反应动力学(Tafel值)和产物选择性对电解液pH值具有显著依赖性. 在酸性pH下Tafel斜率约为120 mV dec^‒1, 在中性条件下大于120 mV dec^‒1, 在碱性条件下, 约为60 mV dec^‒1, 分别对应于质子耦合电子转移(PCET)、Volmer和LH速率模型. 且酸性条件下MF产物选择性对电位也具有显著依赖, 结合动力学结果可以推测, ECH中的氢解反应可能是一种混合机制. 通过增强原位拉曼光谱(SHINERS)进一步观察Au@SiO₂纳米颗粒在糠醛氢解反应中的加氢脱氧行为, 其中关键的脱氧中间体Cu-O_ad仅出现在酸性介质中, 并随反应过电位的增加而显著增加. 总结实验特点: (1) FA和MF是平行生成的; (2)氢解产物MF在酸性溶液中具有明显的pH效应和电位效应; (3)在氢解过程中间体C‒O键直接脱氧. 进一步排除FA中间体脱氢成为MF的所有途径, 并且通过DFT合理化了O_ad中间体通过PCET途径优于H_ad转移途径加氢生成水的过程, 从而证实了酸性环境中生成MF的LH-PCET混合机制, 而LH路径具有较高的反应能垒, 是在质子不足情况下(即在中碱性条件下)没有氢解产物的生成主要原因. 综上, 本文解释了糠醛在Cu电极上的pH诱导选择性机制, 为复杂环境下的ECH过程提供了新的见解, 并拓宽了对生物质衍生油精炼过程中含氧化合物脱氧反应机制的认识.

关键词: 电催化加氢, 生物质, pH依赖性, 机理

Abstract:

The efficient and selective electrocatalytic hydrogenation (ECH) of furfural is considered a green strategy for achieving biomass-derived high-value chemicals. Regulating an aqueous electrolytic environment, a green hydrogen energy source of water, is significant for improving the selectivity of products and reducing energy consumption. In this study, we systematically investigated the mechanism of pH dependence of product selectivity in the ECH of furfural on Cu electrodes. Under acidic conditions, the oxygen atom dissociated directly from hydrogenated furfural-derived alkoxyl intermediates, followed by stepwise hydrogenation until H₂O formation via a thermodynamically favorable proton-coupled electron transfer process, thereby inducing a high proportion of the hydrogenolysis product (2-methylfuran). However, under partial alkaline conditions, furfural could be directly hydrogenated to furfuryl alcohol (selectivity ~98%) due to the high-energy barrier of the deoxidation process via a surface hydride (H_ad) transfer. Our results highlight the vital role of the electrolytic environment in furfural selective conversion and broaden our fundamental understanding of hydrodeoxygenation reactions in ECH.

Key words: Electrocatalytic hydrogenation, Biomass, pH Dependence, Mechanism

周灵, 李莹莹, 逯宇轩, 王双印, 邹雨芹. pH诱导的铜电极上糠醛选择性电催化氢化[J]. 催化学报, 2022, 43(12): 3142-3153.

Ling Zhou, Yingying Li, Yuxuan Lu, Shuangyin Wang, Yuqin Zou. pH-Induced selective electrocatalytic hydrogenation of furfural on Cu electrodes[J]. Chinese Journal of Catalysis, 2022, 43(12): 3142-3153.

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https://www.cjcatal.com/CN/Y2022/V43/I12/3142

图/表 6

Fig. 1. (a) Proposed reaction pathway for the ECH of FF in the aqueous electrolyte on the Cu electrode. (b) Observed FE% of corresponding product and the selectivity after electrolysis on electrodeposited Cu foam electrodes at -20 mA cm-2 for 30 min in phosphate buffers with 25 mmol L-1 FF of various pH electrolytes. (c) LSVs on electrodeposited Cu foam electrodes in pH 2 electrolytes with the addition of 25 mmol L-1 FF or 25 mmol L-1 FA. (d) Electrolyte composition after electrolysis on electrodeposited Cu foam electrodes at -20 mA cm-2 for 30 min in phosphate buffers with 25 mmol L-1 FA in pH = 2 and 8.

Table 1 Reaction pathways of HER and ECH of FF on the Cu electrode in acid and alkaline electrolytes.

Reaction	Mechanism	Possible rate-determining step	Tafel slope (mV dec^-1)	Reaction (acidic solution)	Reaction (alkaline solution)
HER reaction	Volmer-Heyrovsky mechanism	Volmer reaction: electrochemical adsorption	≈ 120	M + H⁺ + e^- ⇌ M-H* (1)	M + H₂O + e^- ⇌ M-H* + OH^- (3)
HER reaction	Volmer-Heyrovsky mechanism	Heyrovsky reaction: Electrochemical desorption	≈ 40	M-H* + H⁺ + e^- ⇌ M + H₂(2)	M-H* + H₂O + e^- ⇌ M + OH^- + H (4)
ECH reaction	PCET mechanism	PCET reaction: electrochemical desorption	≈ 120	M-B* + H⁺ + e^- ⇌ M + BH (5)	M-B* + H₂O + e^- ⇌ M + BH (7)
	LH mechanism	Volmer reaction: electrochemical adsorption	≈ 120	M + H⁺ + e^- ⇌ M-H* (1)	M + H₂O + e^- ⇌ M-H* + OH^- (3)
	LH mechanism	LH reaction: chemical desorption	≈ 60	M-A* + M-H* ⇌ M+AH (6)	M-A* + M-H* ⇌ M + AH (6)

Fig. 2. The FE% of the corresponding product and selectivity during the ECH of FF on electrodeposited Cu foam at varying cathode potentials in pH = 2 (a) and pH = 8 (b) with 30 C charge transferred. (c) Scheme illustrating the LH and PCET mechanisms in the ECH process (A and B represent the organic intermediates to be hydrogenated through the LH or PCET path, respectively). (d) HER LSVs and corrected ECH LSVs recorded with the RRDE at pH = 1.5 and 13. (e) Collected current density from HER LSVs and corrected ECH LSVs recorded with the RRDE for pH = 1.5-4 at -0.6 V and pH = 11.5-13 at -0.4 V. (f) Corresponding Tafel plots of HER and ECH at pH = 1.5-4 and 11.5-13.

Fig. 3. (a) Illustration of the SHINERS detection of the ECH process. In situ SHINERS spectra of the ECH of FF on electrodeposited Cu in phosphate buffers with 25 mmol L?1 FF in pH = 2 electrolytes (b,e), and pH = 13 electrolytes (c,f). (d) Top-view and side-view illustrations of Oad and OHad on the Cu(111) top site, assuming a threefold bridge coordination with the Cu atom. O, red; H, white; Cu, orange spheres.

Fig. 4. (a) Potential energy surfaces of the ECH of FF on the Cu(111) surface for FF conversion to MF and FA. (b) Top and side views of the adsorption pattern of FF on Cu(111). (c) Energetics of the Oad reduction reaction on Cu(111) to form *H2O via the PCET and LH paths.

Fig. 5. Proposed pathways of the ECH of FF on the Cu electrode in acidic electrolytes.

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pH诱导的铜电极上糠醛选择性电催化氢化

pH-Induced selective electrocatalytic hydrogenation of furfural on Cu electrodes

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