催化学报

催化学报

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光热协同催化增强析氢活性

张心怡a,c, 胡科文a,c, 曹爽d,*, 朴玲钰a,b,*   

  1. a国家纳米科学中心, 北京 100190;
    b中国科学院大学材料科学与光电技术学院, 北京 100049;
    c中国科学院大学, 北京 100049;
    d青岛大学化学化工学院, 山东 青岛 266071
  • 收稿日期:2025-09-04 接受日期:2025-10-09
  • 通讯作者: *电子信箱: caoshuang@qdu.edu.cn (曹爽), piaoly@nanoctr.cn (朴玲钰).
  • 基金资助:
    国家自然科学基金(2024YFF0728602); 中国科学院战略性先导科技专项(XDB0770000); 山东省自然科学基金(ZR2022MB028).

Photothermal synergistic catalysis for enhancing hydrogen production activity

Xinyi Zhanga,c, Kewen Hua,c, Shuang Caod,*, Lingyu Piaoa,b,*   

  1. aNational Center for Nanoscience and Technology, Beijing 100190, China;
    bCollege of Materials Science and Opto-Electronics Technology, University of Chinese Academy of Sciences, Beijing 100049, China;
    cUniversity of Chinese Academy of Sciences, Beijing 100049, China;
    dCollege of Chemistry and Chemical Engineering, Qingdao University, Qingdao 266071, Shandong, China
  • Received:2025-09-04 Accepted:2025-10-09
  • Contact: *E-mail: caoshuang@qdu.edu.cn (S. Cao), piaoly@nanoctr.cn (L. Piao).
  • Supported by:
    National Natural Science Foundation of China (2024YFF0728602), the Strategic Priority Research Program of Chinese Academy of Sciences (XDB0770000), and Shandong Provincial Natural Science Foundation (ZR2022MB028).

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摘要： 面对全球能源危机与环境污染, 开发绿色、可持续的氢能制备技术至关重要. 太阳能光催化分解水制氢是一种理想的解决方案, 但传统光催化技术面临严峻挑战: 半导体材料主要利用仅占太阳光谱4%的紫外线, 而对占绝大部分的可见光与近红外光利用效率极低; 同时, “气-液-固”三相反应体系存在传质阻力大、氢气脱附困难等问题, 导致太阳能到氢气的整体转化效率低下. 因此, 开发能够高效利用全光谱太阳能并优化反应过程的新型催化系统, 对推动光催化制氢技术的实际应用具有重大意义.
本研究设计并构建了一种高效、低成本的光热协同催化系统, 通过将弱疏水修饰的多孔板钛矿型TiO2光催化剂负载于碳化木材基底上, 形成PTFE-PB-240-MW复合材料, 并将传统三相反应体系重构为“气-固”两相系统. 该碳化木材基底在1 kW·m-2光照下表面温度可达137.3 °C, 水分蒸发速率高达44.6 kg/(m2·h), 为后续反应提供充足水蒸气. 性能测试结果表明, 该系统在纯水中析氢速率达11.98 µmol/(cm2·h), 在X-3B染料废水中提升至25.82 µmol/(cm2·h), 分别是当前最先进基底支撑型光热纯水分解系统的8‒9倍和无基底光热废水制氢系统的约400倍, 同时能在30 min内完全降解污染物. 机理研究揭示了三重协同增强机制: 碳化木材基底将长波光子转化为热能, 使反应温度稳定在100 °C, 显著降低反应能垒并加速动力学过程; 气-固两相体系有效降低了水分子传输和氢气脱附的传质阻力; PTFE弱疏水改性优化了界面环境, 通过EPR和荧光光谱证实该改性稳定了表面•OH自由基, 从而显著提升析氢反应动力学. 系统在连续运行160 h后仍保持稳定, 经简单再生后使用寿命可延长至500 h.
综上, 本文通过材料创新与反应体系重构, 成功开发出兼具高性能、高稳定性与低成本优势的光热协同催化系统, 实现了太阳能全光谱高效利用与反应过程优化, 为规模化太阳能制氢及环境修复提供了切实可行的技术方案. 该研究不仅展示了光热协同催化在解决能源与环境问题方面的巨大潜力, 也为下一代光催化系统的设计提供了重要借鉴, 对推动光催化技术从实验室走向实际应用具有积极意义.

关键词: 光热协同, PTFE-PB-240-MW, 氢气, 气-固两相系统, X-3B染料废水

Abstract: Photocatalytic water splitting for hydrogen production is regarded as an effective approach to address the energy crisis. Despite its rapid development, challenges such as low overall solar energy utilization efficiency persist, remaining far from meeting industrialization requirements. To overcome these limitations, we developed a highly active and cost-effective photothermal synergistic catalytic system by immobilizing a weakly hydrophobic mesoporous brookite TiO2 photocatalyst on carbonized wood. Through gas-solid interface reconstruction (optimizing the traditional gas-liquid-solid three-phase system into a gas-solid configuration) and catalytic interface optimization (performing weak hydrophobic modification), the system facilitates more favorable water adsorption and efficient H2 desorption. Meanwhile, the elevated reaction temperature accelerates kinetics, providing both thermodynamic and kinetic advantages. This system achieves an exceptional H2 evolution rate of 11.98 μmol/(cm2·h) in pure water and 25.82 μmol/(cm2·h) in X-3B wastewater-surpassing state-of-the-art substrate-supported photothermal systems by 8-9 times in pure water splitting and outperforming non-substrate photothermal wastewater systems by 400-fold. Notably, this process enables simultaneous high-efficiency H2 production and complete pollutant mineralization, offering a dual-benefit solution for sustainable energy and environmental remediation. These findings demonstrate the system’s potential for scalable industrial hydrogen production, bridging the gap between laboratory-scale research and practical applications.

Key words: Photothermal synergistic, PTFE-PB-240-MW, H2, Gas-solid system, X-3B wastewater