高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

亲水性钌/三苯基膦三间磺酸钠盐配合物催化甲酸脱氢的参数依赖性及反应控制研究

袁宁1,2，余睿昕2，杨言言2，杨颂1,3，刘守军1，余钟亮2,4   

  1. 1. 太原理工大学化学与化工学院

    2. 上饶师范学院化学与环境科学学院

    3. 山西省民用洁净燃料工程研究中心 4. 江西省教育厅黑滑石功能材料制备与应用重点实验室

  • 收稿日期:2025-11-04 修回日期:2025-12-10 网络首发:2025-12-17 发布日期:2025-12-17
  • 通讯作者: 余钟亮 E-mail: yzh2401@126.com
  • 基金资助:
    国家自然科学基金（批准号：22169017）资助

Parameter dependence and reaction control in the hydrophilic ruthenium/triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt complex-catalyzed dehydrogenation of formic acid

YUAN Ning1,2, YU Ruixin2, YANG Yanyan2, YANG Song1,3, LIU Shoujun1, YU Zhongliang2,4   

  1. 1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology

    2. College of Chemistry and Environmental Sciences, Shangrao Normal University

    3. Shanxi Engineering Center of Civil Clean Fuel 4. Key Laboratory of Preparation and Application of Black Talc Functional Materials, Jiangxi Provincial Department of Education

  • Received:2025-11-04 Revised:2025-12-10 Online First:2025-12-17 Published:2025-12-17
  • Supported by:
    Supported by the National Natural Science Foundation of China (No.22169017)

PDF (PC)

摘要： 水溶性均相催化剂在甲酸脱氢中具有效率高、响应快等特点。然而，此类催化剂对反应参数变化敏感。本文采用具备商业化应用前景的水溶性钌/三苯基膦三间磺酸钠盐（Ru/m-TPPTS）催化剂，通过改变催化剂浓度、甲酸与甲酸钠的摩尔比（FA/SF）以及甲酸盐阳离子种类等条件，系统性地研究了反应参数对甲酸脱氢性能的影响规律。结果表明：Ru/m-TPPTS催化剂的活性随FA浓度与FA/SF的变化呈“火山形”趋势，在FA浓度为2.4 M、FA/SF比例为6/4的条件下，其TOF达到了2291 h-1（为商用催化剂的5倍）。改变甲酸盐阳离子的种类，发现含有Na+和K+的溶液其脱氢速率要大于含有NH4+的甲酸溶液，其原因是NH4+将体系维持在较低的pH值，抑制了脱氢反应。溶液脱氢速率随催化剂的浓度增加并非线性提升，TOF与催化剂浓度的双对数拟合斜率为0.76，表明该反应并非由单一活性物种主导。基于催化剂对反应条件的高度敏感性的掌握，通过交替添加氢氧化钠（NaOH）和FA，就可以调控水溶性均相催化体系的释氢过程。本研究为水溶性均相催化剂的反应控制与工业应用提供了理论支撑。

关键词: 均相催化剂, 甲酸, 甲酸盐, pH, 反应控制

Abstract: Water-soluble homogeneous catalysts for formic acid dehydrogenation exhibit high efficiency and rapid response. However, such catalysts are relatively sensitive to variations in reaction parameters. In this study, the commercially promising water-soluble ruthenium/triphenylphosphine-3,3',3''-trisulfonic acid trisodium salt (Ru/m-TPPTS) catalyst was employed to systematically investigate the influence of reaction parameters—including catalyst concentration, molar ratio of formic acid to sodium formate (FA/SF), and type of formate cation—on the performance of formic acid dehydrogenation. The results reveal that the activity of the Ru/m-TPPTS catalyst follows a distinct volcano-shaped trend with respect to both FA concentration and the FA/SF ratio. Under optimal conditions of 2.4 M FA and an FA/SF ratio of 6/4, a turnover frequency (TOF) of 2291 h-1 was achieved—five times higher than that of the commercial Ru/m-TPPTS catalyst. Through varying the cationic species of formate, it was discovered that solutions containing Na+ or K+ exhibit a higher dehydrogenation rate compared to those containing NH4+. This difference is attributed to the fact that NH4+ maintains the system at a lower pH, thereby inhibiting the dehydrogenation reaction. Furthermore, the dehydrogenation rate did not increase linearly with catalyst concentration. A double-logarithmic fitting of TOF versus catalyst concentration yielded a slope of n=0.76, suggesting that the reaction is not governed by a single active species. Owing to the high sensitivity of the catalyst to reaction conditions, the hydrogen release process in the water-soluble homogeneous catalytic system was successfully regulated by alternately adding sodium hydroxide (NaOH) and FA. This study provides a theoretical foundation for the reaction control and industrial application of water-soluble homogeneous catalysts.

Key words: Homogeneous catalysts, Formic acid, Formate, pH, Reaction control

中图分类号: 

TrendMD: