木质素模型化合物在Ru@Bi/N-C上的高效电催化还原裂解: 界面和缺陷效应

doi:10.1016/S1872-2067(26)65005-X

催化学报 ›› 2026, Vol. 84: 401-416.DOI: 10.1016/S1872-2067(26)65005-X

木质素模型化合物在Ru@Bi/N-C上的高效电催化还原裂解: 界面和缺陷效应

史经经^a, 卢言菊^b, 王奎^a, 陈祖鹏^b, 徐俊明^a^,^b(), 蒋剑春^a^,^b

^a 中国林业科学研究院林产化学工业研究所, 江苏省生物质能源与材料重点实验室, 生物质化学利用国家工程实验室, 江苏南京 210042
^b 南京林业大学, 江苏省林业资源高效加工利用协同创新中心, 林产化学与材料国际创新高地, 江苏南京 210037

收稿日期:2025-08-13 接受日期:2025-09-16 出版日期:2026-05-18 发布日期:2026-04-16
通讯作者: *电子信箱: xujunming@icifp.cn (徐俊明).
基金资助:
国家自然科学基金(32171713)

Highly efficient electrocatalytic reductive cleavage of lignin model compounds over Ru@Bi/N-C: Interfacial and defect effects

Jingjing Shi^a, Yanju Lu^b, Kui Wang^a, Zupeng Chen^b, Junming Xu^a^,^b(), Jianchun Jiang^a^,^b

^a Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material, Jiangsu Province, National Engineering Lab. for Biomass Chemical Utilization, Nanjing 210042, Jiangsu, China
^b Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing 210037, Jiangsu, China

Received:2025-08-13 Accepted:2025-09-16 Online:2026-05-18 Published:2026-04-16
Contact: * E-mail: xujunming@icifp.cn (J. Xu).
About author:First author contact:Credit author statement
Jingjing Shi: Investigation, Data curation, Validation, Writing - original draft, Visualization. Junming Xu: Resources, Supervision, Writing - review & editing, Project administration, Funding acquisition. Kui Wang: Supervision. Yanju Lu: Supervision. Zupeng Chen: Supervision, Writing - review & editing. Jianchun Jiang: Resources, Supervision, Project administration.
Supported by:
National Natural Science Foundation of China(32171713)

摘要/Abstract

摘要：

木质素由大量苯丙烷单元通过C‒O和C‒C键以无序方式相互连接构成, 其独特的天然结构为高附加值酚类化学品和高热值环烷烃燃料的可持续绿色合成提供了理想原料. 近年来, 凭借环境兼容性和参数精确可调性, 电催化加氢(ECH)技术在木质素高效活化与选择性裂解方面展现出显著潜力. 然而, 木质素连接键的断裂与苯环结构的加氢环化需要克服较高的反应能垒, 导致当前木质素ECH过程存在动力学效率低和反应时间过长的问题. 此外, 剧烈的析氢反应(HER)会降低法拉第效率(FE)并抬高反应电位. 通过精准优化反应微环境及构建高效催化界面位点, 有效调控氢物种迁移路径与反应中间体吸附行为, 是突破木质素ECH技术瓶颈的关键策略

本研究通过在Ru@Bi/N-C催化剂表面进行策略性结构设计, 构建了Bi-Ru界面及相邻的氮缺陷位点. 该设计不仅优化了底物吸附与脱附之间的平衡, 还有效抑制了活性吸附氢的积累, 从而显著降低了木质素模型化合物的电化学加氢脱氧能垒的同时大幅抑制HER. 通过耦合杂多酸(HPW)与六氟异丙醇(HFIP)双相电解质体系, 2-苯氧基-1-苯乙醇的转化率达到93.64%, FE高达91.92%. 此外, 针对一系列单酚类模型化合物实现了超过90%的加氢脱氧效率, 且在连续13次循环实验中未观察到失活现象, 其综合性能优于现有多数先进电催化体系. 同步辐射、原位拉曼及密度泛函理论模拟表明, 液态金属铋的有效涂覆促进了Ru-Bi界面的形成, 并产生大量相邻的氮缺陷位点. Ru-Bi界面抑制了底物在Ru位点上的强吸附, 转而倾向于在相邻氮位点发生有效吸附与快速脱附过程. 此外, Ru-Bi界面的阻塞效应抑制了吸附氢的积累, 确保了在催化剂表面ECH反应动力学优于HER. HPW电解质表现出较低的质子解离能垒, 并能通过其氧化态之间的可逆转换实现电子存储. 在悬浮催化剂表面, 该电解质可携带电子并间接介导电子交换, 从而产生丰富的吸附氢. 这不仅保证了高导电性, 还提升了传质效率. 此外, HFIP可促进底物中羟基的质子化, 有效降低ECH的能垒.

综上, 本研究通过液相涂层处理成功构建了特定界面和邻位位点, 从而能够精确调控底物吸附和氢物种迁移路径. 实现了高FE加氢转化, 显著减少HER发生. 此外, HPW-HFIP系统的开发有效降低了加氢反应能垒, 为木质素ECH微环境设计提供了有价值的见解.

关键词: 木质素电催化加氢, 界面效应, 氢物种迁移通道, 吸附调控

Abstract:

Understanding and regulating the substrate adsorption behavior and hydrogen species (H_spe) migration channels are crucial for achieving efficient lignin electrocatalytic hydrogenation (ECH). This effective Bi-Ru interface and adjacent N-defect sites were constructed on Ru@Bi/N-C catalyst, thereby controllably modulating the blocking and exposure of substrate adsorption sites while establishing ideal H_spe migration pathways. By introducing heteropolyacid (HPW) and hexafluoroisopropanol (HFIP) electrolyte, the conversion of 2-phenoxy-1-phenylethanol attained 93.64%, with Faraday efficiency (FE) of 91.92%. Moreover, the high hydrogenation deoxygenation efficiency (> 90%) was also obtained for phenolic monomers, demonstrating superior performance compared to most advanced electrocatalytic systems. Synchrotron radiation, in-situ Raman, and density functional theory calculations have demonstrated that the Bi-Ru interface obstructed the strong substrates adsorption on the Ru crystal surface, thereby facilitating the adsorption-activation and rapid desorption at N-defect sites. The blocking effect of Bi-Ru interface inhibited the hydrogen evolution reaction while promoting the spillover of adsorbed hydrogen (H_ads) to enable efficient ECH. Additionally, HPW mediated electron transfer could supply abundant H_ads, whereas polar HFIP promoted the protonation of substrate hydroxyl. This research developed a universal strategy for creating an exquisite catalytic network and establishing an optimized electrolyte microenvironment, providing significant insights for the development of highly efficient lignin ECH systems.

Key words: Lignin electrochemical hydrogenation, Interface effect, Hydrogen species migration channel, Adsorption modulation

史经经, 卢言菊, 王奎, 陈祖鹏, 徐俊明, 蒋剑春. 木质素模型化合物在Ru@Bi/N-C上的高效电催化还原裂解: 界面和缺陷效应[J]. 催化学报, 2026, 84: 401-416.

Jingjing Shi, Yanju Lu, Kui Wang, Zupeng Chen, Junming Xu, Jianchun Jiang. Highly efficient electrocatalytic reductive cleavage of lignin model compounds over Ru@Bi/N-C: Interfacial and defect effects[J]. Chinese Journal of Catalysis, 2026, 84: 401-416.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65005-X

https://www.cjcatal.com/CN/Y2026/V84/I5/401

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Fig. 1. (a) Schematic illustration of the value-added utilization of lignocellulosic biomass. The electrocatalytic processes of previously reported lignin dimers (b-1) and monophenolic (b-2). (c) The electrocatalytic strategy of Ru@Bi/N-C put forward in this work for dimer (upper) and monophenol (lower).

Fig. 2. (a) Schematic diagram of Ru@Bi/N-C preparation process. (b) XRD patterns of different catalysts. The representative TEM (c), HRTEM (d,e) images, the FFT derived image corresponding to the rectangular area (f,g), and the corresponding EDS elemental mappings of Ru@Bi/N-C (h?k,l).

Fig. 3. XANES spectra (a) and Fourier transformed EXAFS spectra (b) at Ru K-edge of RuO2, Ru foil, Ru/N-C and Ru@Bi/N-C. (c) Ru K-edge EXAFS (line) and curve fit (points) for Ru/N-C and Ru@Bi/N-C. (d) Wavelet transform of the Ru K-edge for the EXAFS spectra of RuO2 (d-1), Ru foil (d-2), Ru/N-C (d-3) and Ru@Bi/N-C (d-4). Ru 3d (e), Bi 4f (f), C 1s (g), and N 1s (h) XPS spectra of Ru@Bi/N-C. Raman (i) and EPR (j) spectra of N-C-900, Ru/N-C and Ru@Bi/N-C.

Fig. 4. (a) The conversion and FE of different catalysts. (b) The conversion and FE of Ru@Bi/N-C and Ru/N-C at different current densities. (c) The LSV curves of different catalysts. (d) The LSV curves of Ru@Bi1/N-C and Bi+Ru/N-C. (e) Tafel slopes of different catalysts. (f) The relationship between current density and scan rate on Ru@Bi/N-C and Ru/N-C. Bode plots of Ru/N-C (g) and Ru@Bi/N-C (h) without and with 2-phenoxy-1-phenylethanol. (i,j) The free energy diagrams of HER on Ru/N-C and Ru@Bi/N-C. (k) H2-TPD results of Ru/N-C and Ru@Bi/N-C. Reaction conditions: 50 mmol·L?1 substrate, 0.02 g catalyst, 0.1? mol·L?1 HFIP and 0.1 mol·L?1 HPW solution (15 mL), 20 ?mA·cm?2, 60? °C, 2 ?h, 300 ?rpm.

Fig. 5. In-situ Raman spectra of Ru@Bi/N-C (a) and Ru/N-C (b) at different times with applied current density of 20 mA·cm?2. (c) The adsorption model of 2-phenoxy-1-phenylethanol on Ru@Bi/N-C, Ru/N-C and N-C. The adsorption energies of 2-phenoxy-1-phenylethanol (d) and phenol (e) on Ru@Bi/N-C, Ru/N-C, and N-C. Schematic diagram of Hspe migration channel and substrate fracture paths on Ru/N-C (f) and Ru@Bi/N-C (g).

Fig. 6. (a) HPW electrolysis diagram. The LSV curves (b) and Tafel slopes (c) of Ru@Bi/N-C in different electrolyte. (d) The conversion and FE of Ru@Bi/N-C in different electrolyte. (e) The monomer yield of at Ru@Bi/N-C different current densities. (f) Possible reaction pathways for 2-phenoxy-1-phenylethanol.

Fig. 7. (a) The conversion and FE of Ru@Bi/N-C for 13 successive electrolysis cycles. Reaction conditions: substrate (50 mmol·L?1), 0.02 g catalyst, 0.1? mol·L?1 HFIP and 0.1 mol·L?1 HPW solution (15 mL), 20 ?mA·cm?2, 60? °C, 2 ?h, 300 ?rpm. The representative TEM (b), HRTEM (c) image, and the corresponding EDS elemental mappings (d?g) of the used Ru@Bi/N-C, respectively. (h) XRD pattern of the used Ru@Bi/N-C. XPS total (i) and Ru 3d (j) spectra of the used Ru@Bi/N-C. (k) The ECH of monophenolic model compounds with varying substituents. Reaction conditions: substrate (10 mmol·L?1), 0.02 g catalyst, 0.1? mol·L?1 HFIP and 0.1 mol·L?1 HPW solution (15 ?mL), 20 ?mA·cm?2, 60? °C, 4 ?h, 300 ?rpm.

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木质素模型化合物在Ru@Bi/N-C上的高效电催化还原裂解: 界面和缺陷效应

Highly efficient electrocatalytic reductive cleavage of lignin model compounds over Ru@Bi/N-C: Interfacial and defect effects

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