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

Parameter Dependence and Reaction Control in the Hydrophilic Ruthenium/Triphenylphosphine-3，3′ ， 3″-trisulfonic Acid Trisodium Salt Complex-catalyzed Dehydrogenation of Formic Acid

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, 系统考察了催化剂浓度、 甲酸(FA)与甲酸钠(SF)的摩尔比及甲酸盐阳离子种类等条件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 摩尔比的变化呈“火山形”变化, 在FA 浓度为2.4 mol/L， FA/SF摩尔比为6/4的条件下, 转化频率(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⁺的甲酸盐溶液脱氢速率要大于含有NH₄ ⁺的甲酸盐溶液, 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浓度的增加并非线性提升, 产气速率(r′)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, 通过交替添加氢氧化钠和FA, 就可以调控水溶性均相催化体系的释氢过程. 该研究结果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.

Abstract

The water-soluble homogeneous catalyst of formic acid dehydrogenation exhibits high efficiency and rapid response. However, these catalysts are more sensitive to changes in reaction parameters. Here, we systematically investigate the influence of reaction parameters, including catalyst concentration, molar ratio of formic acid (FA) to sodium formate (SF) and type of formate cation on the performance of formic acid dehydrogenation, by employing a commercially promising water-soluble ruthenium/triphenylphosphine-3,3′ , 3″-trisulfonic acid trisodium salt (Ru/m-TPPTS) catalyst. The results reveal that the activity of the Ru/m-TPPTS catalyst follows a volcano-type dependence on the FA concentration and FA/SF ratio. Its turnover frequency (TOF) reached 2291 h⁻¹ (five times that of the commercial catalyst Ru/m-TPPTS) under optimal conditions of 2.4 mol/L FA and an FA/SF ratio of 6/4. By altering the type of formate cation, it was found that solutions containing NH₄ ⁺ exhibited lower hydrogen production rates compared to those containing Na⁺ or K⁺. This behavior is attributed to the ability of NH₄ ⁺ to maintain the system at a lower pH value, suppressing the dehydrogenation reaction. Furthermore, the dehydrogenation rate did not increase linearly with catalyst concentration. A double-logarithmic fitting of gas production rate (r′) versus catalyst concentration yielded a slope of n=0.76, suggesting that the reaction is not governed by a single active species. Based on the high sensitivity of the catalyst to reaction conditions, the hydrogen release process was effectively regulated by alternately adding sodium hydroxide (NaOH) and FA in the water-soluble homogeneous catalytic system. This study provides a theoretical foundation for the reaction control and industrial application of water-soluble homogeneous catalysts.

关键词

均相催化剂 / 甲酸 / 甲酸盐 / pH值 / 反应控制

Key words

Homogeneous catalysts / Formic acid / Formate / pH value / Reaction control

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基金资助

国家自然科学基金(22169017)