Pt/TiO₂电催化愈创木酚加氢脱氧: 反应底物的吸附及氢溢流的调控

doi:10.1016/S1872-2067(26)65133-9

摘要/Abstract

摘要：

化石资源长期过度开采导致能源危机与环境压力加剧, 发展可再生资源的高效转化路径具有重要意义. 木质素作为潜在的芳香化合物来源有望在化工合成领域发挥重要作用, 然而其选择性转化制大宗化学品仍面临C-O键活化难、反应路径复杂等问题. 愈创木酚(GUA)是典型木质素模型分子, 其加氢脱氧(HDO)可制备多种高附加值精细化学品. 其热催化HDO往往依赖较高的反应温度和压力及外加氢源, 因而能耗较高. 相比之下, 电催化路径可在相对温和条件下运行, 无需外加氢气, 为木质素衍生物绿色转化提供了新的思路. 然而, 如何调控反应选择性并抑制析氢等副反应仍是电催化HDO领域亟待解决的问题.
本工作采用H₂预还原处理构筑缺陷型Pt/TiO₂电催化剂, 用于GUA电催化HDO制KA油(环己醇与环己酮混合物), 实现了70%的KA油选择性. 研究发现, 适度的H₂还原处理可调控Pt/TiO₂界面结构与表面缺陷分布, 赋予催化剂独特的电子性质与吸附能力, 其中Pt/TiO₂-400R表现出最优的催化性能。一方面, 适当温度条件下H₂预还原处理增强了Pt表面对GUA分子的吸附能力, 更利于甲氧基的活化; 另一方面, TiO₂载体表面丰富的缺陷促进了金属-载体界面的氢溢流效应, 使界面活性氢物种更易生成并迁移. 在电催化条件下, 界面氢溢流与质子耦合电子转移(PCET)过程协同作用, 既促进了芳环的部分加氢以及C-O键的断裂, 又有效抑制竞争性的析氢和芳香环饱和副反应. 金属-载体相互作用通过调控吸附构型及反应中间体转化速率, 在选择性调控中发挥关键作用. 与传统碳载体催化剂相比, Pt/TiO₂界面结构为氢物种迁移与反应路径调控提供了更有利的环境, 从而实现了目标产物KA油的选择性的提升. 通过对同一催化剂电催化、热催化反应的对照研究发现, Pt是实现高效加氢脱氧反应的主活性中心, 但是氢溢流效应对反应也起到重要的促进作用, 尤其是在电催化反应过程中. 本研究结果表明, 合理设计负载型电催化体系并强化界面氢溢流效应, 是调控芳香族电催化加氢选择性的有效策略.
综上, H₂还原Pt/TiO₂电催化剂通过构建缺陷富集的金属-载体界面, 实现了界面氢溢流与PCET过程的协同调控, 从而提高了GUA电催化HDO制KA油的性能. 本研究为负载型电催化剂的结构设计提供了新的思路, 也为木质素衍生芳香族化合物的绿色电催化转化提供了理论参考.

关键词: 电催化加氢脱氧, 生物质, Pt纳米粒子, C-O键裂解, 氢溢流

Abstract:

The synthesis of KA oil (a cyclohexanone-cyclohexanol mixture) from guaiacol through mild electrocatalytic approach represents a sustainable strategy for biomass valorization. Herein, we report the electrocatalytic conversion of guaiacol to KA oil over the reduced Pt/TiO₂ catalysts. The TiO₂-induced hydrogen spillover effect facilitates strategic modulation of H_ads(H*) coverage on Pt surfaces, thereby effectively suppressing competitive aromatic ring hydrogenation and excessive hydrogen evolution reactions. Comparative studies of electrocatalysis and thermocatalysis have demonstrated that Pt active sites serve as the dominant catalytic centers. However, H spillover significantly influences reactivity and selectivity, particularly in the electrocatalytic pathways. The electrocatalytic system demonstrates preferential C-O bond cleavage with KA oil selectivity around 70%. This work provides valuable insights into the regulation of metal-support interactions in the design of electrocatalysts.

Key words: Electrocatalytic hydrodeoxygenation, Biomass, Pt nanoparticles, C-O cleavage, H spillover

赵一玮, 金祖航, 陶城, 杜锐, 石永政, 张弨. Pt/TiO₂电催化愈创木酚加氢脱氧: 反应底物的吸附及氢溢流的调控[J]. 催化学报, 2026, 88: 393-407.

Yiwei Zhao, Zuhang Jin, Cheng Tao, Rui Du, Yongzheng Shi, Chao Zhang. Electrocatalytic hydrodeoxygenation of guaiacol on Pt/TiO₂: The modulation on guaiacol adsorption and H spillover[J]. Chinese Journal of Catalysis, 2026, 88: 393-407.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65133-9

https://www.cjcatal.com/CN/Y2026/V88/I9/393

图/表 11

Fig. 1. (a) Conversion and selectivity of the Pt/TiO2 catalysts. (b) TOF of the Pt/TiO2 catalysts. (c) Product selectivity and GUA conversion rate (10 mmol L-1) over the Pt/TiO2-400R catalyst at different current densities. (d) The FE of products on Pt/TiO2-400R catalyst at different current densities. Reaction conditions: 1.0 mg catalyst, 10 mmol L-1 GUA, 10 mL 0.2 mol L-1 HClO4, -20 mA cm-2, 50 °C, 2 h.

Fig. 2. TEM images of Pt/TiO2-200R (a), Pt/TiO2-400R (b), Pt/TiO2-600R (c), Pt/SiO2-200R (d), Pt/SiO2-400R (e), Pt/SiO2-600R (f), Pt/C-200R (g), Pt/C-400R (h), and Pt/C-600R (i) catalysts.

Fig. 3. (a) XRD patterns of Pt/TiO2 catalysts calcined at 400 °C in air followed by subsequent hydrogen reduction at temperatures of 200, 400, and 600 °C. XPS spectra of Pt 4f (b), O 1s (c), and Ti 2p (d) for Pt/TiO2-200R, Pt/TiO2-400R, and Pt/TiO2-600R.

Fig. 4. Nyquist plots (a) and OCP curves (b) of Pt/TiO2-200R, Pt/TiO2-400R, and Pt/TiO2-600R. (c) LSV curves of Pt/TiO2-400R in the presence and absence of 10 mmol L-1 GUA. (d) Tafel slopes derived from polarization data for Pt/TiO2-400R. Reaction conditions: 1.0 mg of catalyst, 10 mmol L-1 of GUA, 10.0 mL of 0.2 mol L-1 HClO4, 50 °C.

Fig. 5. (a) H2-TPD profiles of Pt/TiO2 catalysts reduced at different temperatures. (b) H2-TPD profiles of the Pt-based catalysts on different supports.

Fig. 6. In-situ FTIR spectra of GUA on Pt/TiO2-200R (a), Pt/TiO2-400R (b), and Pt/TiO2-600R (c) catalysts. (d) Adsorption spectra of GUA on Pt/TiO2-200R (black), Pt/TiO2-400R (red), Pt/TiO2-600R (blue) after 180 min.

Fig. 7. Comparative GUA HDO over Pt/TiO2 catalysts. (a) Product selectivity and GUA conversion for Pt/TiO2-400R under electrocatalytic (solid cylinders) vs. thermocatalytic (hollow cylinders) conditions. (b) Product selectivity and GUA conversion over Pt/TiO2 catalysts reduced at 200-600 °C under electrocatalytic (solid cylinders) and thermocatalytic (hollow cylinders) regimes. Reaction conditions: 50 °C, 2 h, HClO4 or H2SO4 solution of equivalent pH. Electrocatalysis: 1 mg catalyst, 10 mmol L-1 GUA, 10 mL 0.2 mol L-1 HClO4, -20 mA cm-2. Thermocatalysis: 2.0 mg catalyst, 20 mmol L-1 GUA, 1 MPa 20% H2/Ar, 10 mL 0.2 mol L-1 HClO4.

Fig. 8. Possible reaction mechanism for the electrocatalytic HDO of GUA on Pt/TiO2-400R.

Table 4 Calculated adsorption configurations and energetics of hydrogen species on Pt/TiO2(101) and oxygen-deficient Pt/TiO2(101)-Ov surfaces. Blue, gray, red, and pink spheres represent Pt, Ti, O, and H atoms, respectively.

System	Item	ΔE (eV)	ΔE (KJ mol^-1)
Pt/TiO₂(101)	Slad-H1*	2.22	2114.42
Pt/TiO₂(101)	Slad-H2*	2.22	2114.42
Pt/TiO₂(101)-O_v	Slad-H1*	2.17	210.33
Pt/TiO₂(101)-O_v	Slad-H2*	2.17	210.33

Fig. 9. (a) Stability assessment of the Pt/TiO2-400R catalyst via five consecutive GUA conversion cycles under a constant current density of -20 mA cm-2. (b) LSV curves of Pt/TiO2-400R and used-Pt/TiO2-400R-5 runs in 0.2 mol L-1 HClO4 electrolyte containing 10 mmol L-1 GUA. (c) XRD patterns of Pt/TiO2-400R and used-Pt/TiO2-400R-5 runs. (d) TEM images of used-Pt/TiO2-400R-5 runs. Reaction conditions: 1.0 mg of catalyst, 10 mmol L-1 of GUA, 10.0 mL of 0.2 mol L-1 HClO4, -20 mA cm-2, 50 °C, 2 h.

Fig. 10. (a) H2-TPD profiles of Pt/TiO2-400R and used-Pt/TiO2-400R-5 runs. XPS spectra of Ti 2p (b), O 1s (c), and Pt 4f (d) for fresh Pt/TiO2-400R and used-Pt/TiO2-400R-5 runs.

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